Aliphatic copolyester resin, a preparation method, an aliphatic polyester resin composition, uses thereof, a coating composition, a particle-state composition for agriculture and gardening coated by degradabel layer

ABSTRACT

This invention relates to aliphatic polyesters having a controlled thermal decomposition, hydrolizability, and biodegradability, in which OH terminals and COOH terminals are decreased through a ring-opening polymerization of a lactone and lactide by a mono alcohol or a metal alkoxide, or by decreasing both terminals through combining polymer terminals with diisocyanate. From a composition containing the polyesters, this invention provides a controlled release composition for agriculture. From a resin primarily containing fatty acid cellulose ester derivatives, this invention provides a base film for a marking film without volatilization and plasticizer migration problems; a picture image formable heat-sensitive transfer recording material with excellent strippability, coloring concentration, and brightness; a conductive coating composition with excellent storage stability, adhesion, and conductivity; a single-liquid type coating for a moisture-curable graft copolymer, and a non-toxic and non-irritating coating composition with excellent dryability. The copolymers of this invention also have excellent heat and impact resistance.

TECHNICAL FIELD

No. I of the present invention relates to aliphatic polyesters having acontrolled thermal decomposition property, hydrolyzability, andbiodegradability, and a method for the preparation thereof. In moredetail, it relates to aliphatic polyesters which comprise polymerizing acyclic ester monomer using a monoalcohol as an initiator, aliphaticpolyesters in which terminal groups are modified, and a method for thepreparation thereof.

Further, No. II of the present invention relates to a particle-statefertilizer coated by a degradable thin layer which comprises abiodegradable terminal-controlled aliphatic polyester which comprises amonomer unit of at least any one of a lactone and lactide, in whichproportion of the number of an alcohol-terminal is not more than 50%and/or proportion of the number of a carboxylic acid-terminal is notmore than 30%.

Still further, No. III of the present invention relates to aparticle-state fertilizer coated by a degradable thin layer whichcomprises a biodegradable cyclic ester-modified cellulose ester.

The thin layer to be employed for the particle-state fertilizer of thepresent invention is decomposed by microorganisms in soil, and it doesnot finally remain in soil. Further, in the thin layer, a variety ofadditives and chemicals can be added for adjusting elution of theparticle-state fertilizer.

Also, No. IV of the present invention relates a base film for a markingfilm which comprises resins primarily containing a specified celluloseester-based derivative. In more detail, it relates to a base film for amarking film which comprises resins primarily containing a specifiedcellulose ester derivative in which a cyclic ester is ring-openinggraft-polymerized.

Also, No. V of the present invention relates a heat-sensitive transferpicture image recording material. In more detail, it relates to aheat-sensitive transfer picture image recording material having anexcellent strippability from a heat-transfer sheet containing asublimatable dye, in which concentration of coloration is high and, inwhich there can be formed a recorded picture image having an excellentbrightness, and relates to a method for the preparation thereof.

Also, No. VI of the present invention relates a heat-sensitive transferrecording material and, in more detail, it relates to a heat-sensitivetransfer recording material in which there are not caused a stickingphenomenon and a blocking phenomenon, and which is excellent in storagestability and printing quality.

Also, No. VII of the present invention relates a conductive coatingcomposition. In more detail, it relates to a conductive coatingcomposition which comprises a mixture of a resin for a conductivecoating containing a cellulose ester derivative obtained by aring-opening graft-polymerization of cyclic esters to a cellulose esterhaving hydroxy groups with a conductive pigment composed of a mixtureconsisting of a conductive carbon black and a scaly graphite.

Also, No. VIII of the present invention relates a moisture-curable graftcopolymer which is useful as a coating for car parts, construction, andrepairing, and relates to a coating composition containing thereof.

And also, No. IX the present invention relates a lactide/lactonecopolymer and a method for the preparation thereof and, in more detail,it relates a lactide/lactone copolymer in which an average continuouschain length is controlled in respective units of the copolymer, andrelates to a method for the preparation in which an average continuouschain length can be freely controlled in respective units of thecopolymer.

TECHNICAL BACKGROUND

(The No. I of the Present Invention)

In recent years, treatment of waste plastics is becoming a socialproblem, and recycling of plastics material and biodegradable plasticsare paid attention. An aliphatic polyester resin is one of materialswhich are largely desired owing to biodegradability.

As one of the aliphatic polyester resins which are industriallyproduced, a polycaprolactone is known. A polycaprolactone having a lowmolecular weight is an important material as a raw material for apolyurethane, a paint, and a coating agent. A polycaprolactone having ahigh molecular weight is employed as a molded article such as a compostbag, fishing lines, tees for golf, and a hot-melt adhesive, etc. owingto biodegradability.

Further, the aliphatic polyester has been widely employed as a preferredmaterial also in uses such as a use for molding various portions ofhuman body and a use by fitting to human body. For example, a gyps formedical care (JP-A-58081042 Official Gazette) and a face mask forirradiating radiation rays (JP-A-60215018 Official Gazette) have beenknown.

It is known that although such the aliphatic polyester has a peculiarthermally-decomposing property, hydrolyzability, and biodegradability,etc., respectively, in the case of the uses, thermally-decomposingproperty, hydrolyzability, and biodegradability, decomposition ordegradation rate become important depending upon the uses thereof,accordingly, their properties can be modified by variouscopolymerization.

For example, the thermally-decomposing property, hydrolyzability, andbiodegradability of the aliphatic polyesters are controlled by acopolymerization of a lactone with a lactide, a copolymerization of alactone with a glycolide, a copolymerization of a lactone with acarbonate, a copolymerization of a lactone with a cyclic ester, acopolymerization of a lactone with a lactam and, or modification ofcomposition ratio, etc.

Still further, in a polycondensation type polyester, it is tried tohighly-polymerize by an isocyanate compound (JP-A-04189823 andJP-A-05178955 Official Gazettes). However, since a polymer having asufficiently high molecular weight can be obtained without acrosslinking reaction in the aliphatic polyester which is obtained bythe ring-opening polymerization such as in the present invention, therewas not investigated a reaction with an isocyanate compound, etc.

In the case of controlling the thermally-decomposing property,hydrolyzability, and biodegradability of the aliphatic polyesters,although there can be obtained a polymer having a desiredthermally-decomposing property, hydrolyzability, and biodegradability bycopolymerization, there is a problem that the copolymerization alsoaffects to various other physical properties, resulting in that therecannot be obtained a target polymer.

(The No. II of the Present Invention)

Hitherto, for the purpose of manifestation of a fertilizing effectdepending upon growth of farm products, there have been developedvarious fertilizing effect-controllable fertilizers.

Particularly, there have been disclosed and commercially-supplied aparticle-state fertilizer in which a coating material is coated on thesurface. As described in JP-B-95000505 Official Gazette, there have beenproposed various fertilizing effect-controllable fertilizers in, forexample, U.S. Pat. No. 3,295,950, JP-B-65028927, JP-B-69028457, GBPatent 815829, JP-B-62015832 and JP-B-67013681 Official Gazettes.However, it is taught that it is difficult to adjust an elution rate offertilizing components in all the fertilizing effect-controllablefertilizers.

On the other hand, JP-B-85021952 and JP-B-85003040 Official Gazettesdisclose a method for forming a thin layer in which there is employed acoating material primarily containing a polyolefin, and in the case ofcoating the surface of particle-state fertilizers, a hot air is blown todry together with spraying a solution of the coating material over theparticle-state fertilizers. It is taught that the method ischaracterized in that an elution rate of the fertilizers can becontrolled, and the above-described method is widely put into practice,in which a thin layer is formed over the surface of the particle-statefertilizers.

Further, JP-B-85003040 and JP-A-55901672 Official Gazettes, etc. showthat a function for controlling elution is maintained by dispersinginorganic powders such as talc and sulphur into a thin layer of thepolyolefin-based resin and, at the same time, there is accelerated thedegradation or decomposition of residual thin layer after elution.

In the particle-state fertilizers which have been conventionallyproposed, the coating layers do not cause degradation or decomposition,and even though those caused the degradation, those remain in soil,resulting in that it is anxious that those produce pollution in thegrowth of farm products, soil circumstances, and water for irrigationand river around fields.

From that reason, there has been intensively desired a particle-statefertilizer in which a thin layer has degradability and a duration periodof a fertilizing effect can be controlled.

In such the degradable thin layer, degradability means degradation bylight, oxygen, and microorganisms, etc.

Particularly, in the conventional particle-state fertilizer coated, itis difficult to control the elution rate of fertilizing components, andthere has been a drawback that the fertilizing period is apt to bereadily affected by circumstances such as weather and soil. Further, itis pointed that the thin layer after elution of the fertilizingcomponents remain in soil over a long time of period withoutdegradation.

For that reason, utilization of biodegradable resins has been oftentried and, for example, JP-A-07033576 Official Gazette states acombination of a polycaprolactone, a polylactic acid, or an aliphaticpolyester compound with cellulose derivatives, low molecular weightpolyethylenes, and paraffins, etc. However, since the polycaprolactoneto be employed in the case has a melting point of 60° C., blocking isoccasionally caused in transport or storage of products.

Further, the above-described JP-B-95000505 also likewise disclosesparticle-state fertilizers coated by a polycaprolactone.

However, in the coating material such as the polycaprolactone andpolylactic acid, since degradation of the coating materials is tooquick, those are not preferred in the case of employing as agradually-dischargeable fertilizer.

(The No. III of the Present Invention)

In addition to the above-described problems relating to the coatingmaterials, since the polylactic acid and the aliphatic polyester have alow solubility to solvents, it is difficult to put into practice,resulting in being not sufficiently satisfied.

Further, in JP-A-11116371 Official Gazette, there is proposed the use ofa cellulose acetate having a low substitution degree which is poor insolubility and, in the case of employing coating for a particle-statefertilizer, trichloroethylene and tetrahydrofran are employed assolvents. Accordingly, handling and price of the solvents have beenproblematic.

(The IV of the Present Invention

A marking film means a film which is stuck on wall surface of transportvehicles, buildings, and electric-light poles, etc. in which a printedand ink layer are formed on one surface of a base film for (wappen) toprepare various patterns, and a pressure sensitive adhesive layer isformed on other surface, which is employed by sticking it at surface ofa large-size outdoor advertisements, road signs, signboards on streets,company trade names, etc., and clothes, daily necessaries, and toys,etc. It is pais attention owing to effectively setting by only stickingin place of a method for individually coating a paint. As a base filmwhich has been conventionally employed for a marking film, although apolyester film and a polyurethane film are also known a little, a filmmade from a polyvinylchloride-based resin is typical in view ofweatherability, total properties in use (that is, characteristicsdepending upon elasticity, a readily sticking property onto a curvedsurface, a readily sticking property of a curved film onto a plainsurface, and bulkiness of a film), and costs.

The vinylchloride-based resin is excellent in various properties such asphysical properties, weatherability, film formability and printingapplicability, and which has been preferably employed as a base filmmaterial for the marking film.

In the vinylchloride-based resin which is a typical example as describedabove, polymerization degree is preferably 300-2000, and more preferably600-1500, and a polyvinylchloride homopolymer resin or a copolymer resinof vinylchloride monomer with various monomers such as an olefin-based,diene-based, halogenated vinyl-based, (meth)acrylic ester-based, vinylester-based, vinyl ether-based, and styrene-based monomers.

Incidentally, as one example of the marking film and use modes thereof,there is exemplified a rolled marking film in which there is prepared abase film having 50 μm for the marking film of the vinylchloride resincast by a plastisol method, and desired durable patterns, etc. areprinted on one surface, and optionally, a clear ink is over-printed togive a high durability and, an acrylic-based pressure sensitive adhesiveis coated in the thickness of approximately 30 μm on another surface,and optionally, a releasing film is laminated as a backing film. It isstuck on surface of the body of a car, etc., stripping off the releasingfilm at a sticking place after forming a cutting mark line in order tocut it into a desired shape by a hand-cut, computerized machine-cut, andpunching cut.

In the meantime, it is reported that the above-describedpolyvinylchloride-based resin which has been preferably employed has alarge possibility that it produces harmful substances such as dioxineduring burning and dumping, and as a result, a research for substituteresin materials is in progress.

As one of the substitute resins, there are paid attention a celluloseester, for example, a cellulose acetate, a cellulose acetate butylate, acellulose acetate propionate which are all a cellulose derivative, andwhich satisfy a variety of properties to be required such as excellenttoughness, glossiness, transparency, oil resistance, and weatherabilityas a resin for the marking film.

However, if those are thermally melted alone, discoloration anddecomposition are simultaneously caused and, further, even though thereis applied a so-called block method in which the above-describedcellulose derivatives are dissolved, kneaded, compressed, and molded toprepare a sheet, there cannot be obtained a resin having an excellentfluidity in heating and a plasticizing property without the addition ofa plasticizer. In the case, as a plasticizer, there are employed aphthalate (for example, dimethyl phthalate, diethyl phthalate, dibutylphthalate, butylbenzyl phthalate, and ethylphthalyl phthalate ethylglycolate, etc.), a trimeritate (for example, trimethyl trimeritate,triethyl trimeritate, and 2-ethylhexyl azelate, etc.), a normalphosphate (for example, tributyl phosphate, cresyl diphenyl phosphate,and 2-ethylhexyl diphenyl phosphate, etc.), and a licinolate (forexample, methyl acetyl licinolate), etc.

However, the cellulose esters containing the plasticizers have a problemthat a softening point becomes too low.

Further, since the cellulose derivatives such as the cellulose estersare usually strong in polarity, there must be selected a plasticizerhaving a strong polarity. However, as a plasticizer which satisfies widerange properties, compatibility, a plasticizing effect, a hightransparency, non-volatility, and a non-migrating property, aconventionally known plasticizer having a low molecular weight is knownalone, and the plasticizer is apt to readily volatile during molding orafter molding. Accordingly, it has a problem that a working circumstanceduring molding becomes worse and dimensional stability lowers in amolded article.

Further, the plasticizer migrates toward a pressure sensitive adhesivelayer or a printing surface in the marking film, resulting in that anadhesive power lowers in the former and a stain by dust sticking iscaused in the latter.

As a result, there is limited the use of a low molecular weightplasticizer for the cellulose derivatives such as the cellulose esters,etc., and it is an existing circumstance that it obstructs anenlargement of uses for a film or a sheet made by the materials,particularly, the use for the marking film, etc.

In order to overcome the limitation in use of the low molecular weightplasticizer, for example, JP-B-68016305 Official Gazette discloses atechnology in which there is added a high molecular weight plasticizerwhich is a polyester having an average molecular weight of 700-4000obtained from a cellulose acetate which is a fatty acid cellulose ester,a glycol, and an aliphatic dibasic acid. The plasticizer is excellent incompatibility with a cellulose acetate having an acetylated degree ofnot less than 52% (substitution degree of not more than 2.2).

Further, U.S. Pat. No. 3,781,381 Specification discloses a technology inwhich a polymer from a cyclic monomer such as ε-caprolactone is added toa cellulose acetate (substitution degree of 2.5) which is a celluloseester.

Still further, U.S. Pat. No. 4,731,122 Specification discloses athermoplastic resin composition in which a cellulose acetate butylateand a cellulose acetate contain tributyl citrate, triethyl citrate, anda polyethylene glycol.

However, the above-described high molecular weight plasticizer is stillinsufficient in compatibility with the cellulose ester and,particularly, in the case that it is applied to a cellulose ester havinga low substitution degree, it is difficult to prevent that it bleeds outof a molded article, and it volatilizes from a molded article, resultingin that it adversely affects to physical properties such as an outerappearance of a molded article which includes a decrease of transparencyby phase separation, and a decrease of a plasticizing effect.

(The No. V of the Present Invention)

As a heat-transfer method for a picture image, various methods have beenconventionally known and, for example, there is proposed a method inwhich a variety of full-color picture images are thermally formed on apicture image recording sheet by bringing into contact aheat-transferable sheet in which a recording agent such as asublimatable dye is carried on a base material sheet (for example, apolyester film, etc.) with a picture image recording sheet having a dyereceiving layer on a material (for example, paper and plastic film,etc.) to be transferred which is capable of dying by using asublimatable dye.

In the method, a thermal head of a printer is employed as a heatingmeans, and a great many of color dots including 3 or 4 colors aretransferred to a picture image recording sheet by heating for anexceedingly short time of period, resulting in that a variety offull-color picture images are thermally reappeared on a recording sheet.Thus-formed picture image is very distinct because a dye is employed asa coloring material, and it is excellent in transparency. Accordingly, apicture image obtained is excellent in repeatability of a medium colorand a contrast, and there can be formed a high-quality picture imagewhich is much for a full-color photograph.

In the heat transfer method, there is important not only a constructionof a heat-transferable sheet but also a construction of a picture imagerecording sheet. As the picture image recording sheet by aheat-sensitive transfer, there has been known a sheet in which there isformed a picture image recording layer using, for example, apolyester-based resin, a vinyl resin containing halogens such as apolyvinyl chloride-based resin, a polycarbonate-based resin, a polyvinylbutylal-based resin, an acrylic-based resin, a cellulose-based resin, anolefin-based resin, and a styrene-based resin, etc.

In such the picture image recording sheet by a heat-sensitive transfer,as a means by which a dyeing property becomes excellent in thesublimatable dye to be transferred, there is a method for forming a dyereceiving layer using a resin having an excellent dyeing property.

For example, JP-A-62211195 Official Gazette proposes a picture imagerecording sheet by a heat-sensitive transfer in which a picture imagerecording layer having a high surface smoothness is formed by a mixturecontaining a pigment and a resin which can be readily dyed such as apolyester, an epoxy resin, and a polystyrene. In the JP, it is describedthat the resin which can be readily dyed may be a water soluble-type andan emulsion type one.

However, the resin which can be readily dyed by a dye has a lowsoftening point and, in the case that a dye-receiving layer is formed inthe heat transferable picture image recording sheet using such theresins, the dye-receiving layer and the heat-transfer sheet are adheredto each other by heat of a thermal head during forming a picture imageand, when those are stripped from each other, there is caused a problem(a so-called abnormal transfer) that a dye layer in the heat-transfersheet is entirely transferred onto the picture image recording sheet byfusing each other. Also, as a method for improving a dye-affinity in adye, there are a method in which a plasticizer is contained in thedye-receiving layer and a method for improving a diffusible property inthe dye of heat-transfer. However, a picture image formed blots andstorage property is low.

JP-A-62222895 Official Gazette discloses a picture image recordingmedium in which a dyeing layer in the picture image recording mediumwhich is a sublimatable heat-sensitive type one contains anacrylic-based polymer and a surface improver having a fluorine-based orsilicone-based graft or block structure.

JP-A-06024152 Official Gazette proposes that a dye receiving layer in apicture image recording medium which is a sublimatable heat-sensitivetype one is formed by a composite polymeric water-based based dispersionin which a core-shell structure is formed by a polymer of a copolyesterresin having at least one polar group with a copolymerizable unsaturatedcompound. However, in the picture image recording medium, it isdifficult to improve a coloring concentration and clearness of a pictureimage while elevating a strippability from a heat-transfer sheet. Asdescribed above, when improving a dye-affinity of a dye receiving layer,a strippability lowers and, when intending to improve the strippabilityand storage stability by forming a picture image recording layer using aresin in which a dye absorbed is not apt to migrate through the dyeabsorbing layer, dye-affinity of the dye becomes lower, resulting inthat there cannot be formed a picture image having a high concentrationand high clearness.

(The Sixth Aspect of the Present Invention)

In a heat-transfer recording method, a printing is recorded on a paperto be transferred as follows. First of all, the paper to be transferredis brought into contact with a heat-transferable ink layer in aheat-transfer recording medium composed of a substrate and theheat-transferable ink layer which is arranged on the surface of thesubstrate under pressure, and then, a thermal head is brought intocontact with an opposite surface (back surface) of the heat-transferableink layer in the substrate. Subsequently, the thermal head is heated bysupplying a pulse-state signal current into the thermal head and, theheat-transferable ink layer is melted or sublimated by heating.

In a thermally melt type transfer recording method, a picture image isrecorded as follows. In the case of black painting, there is employed aheat-transfer recording medium in which carbon black is added to an inklayer and, in the case of color printing, a heat-transfer recordingmedium composed of three primary colors such as yellow, magenta, andcyan are separately prepared and, the three primary colors aretransferred in order onto the same paper to be transferred,respectively.

On the other hand, in a sublimation type heat-transfer method, acontrast-controlled printing can be readily conducted while controllingthe amount of an ink which sublimates by a heat amount from a thermalhead. In order to print a picture image with a high concentration, inputvoltage is elevated or input time of period of an electric current pulseis lengthened and, in order to print a picture image with a lowconcentration, input voltage is lowered or input time of period of anelectric current pulse is shortened. A color printing can be conductedby the same method as in the thermally-melting type method, and a colorprinting having a high contrast can be conducted by changing quantity ofheat on the thermal head.

In the mean time, as a substrate for a thermal melting or a sublimationtype heat-transferable recording medium, there has been conventionallyemployed a plastic film such as a polyethylene terephthalate (PET).Herein, the plastic film such as the PET occasionally fusedly-adheres toa thermal head by melting in a contact portion to the thermal headbecause of heat of the thermal head during transferring, resulting inthat the recording medium cannot become transferred with a stable speed.

The phenomenon (a sticking phenomenon) not only remarkably lowers aprinting quality but also causes a significant noise when thefusedly-adhered film is stripped off from the thermal head, and allowsto stop transferring of the recording medium, or occasionally causes afracture of the substrate. In order to prevent the sticking phenomenon,there are proposed a variety of methods for forming a thermallyresistible protecting layer at one surface (a surface bringing intocontact with the thermal head which is an opposite side of aheat-transferable ink layer) in the substrate.

For example, JP-A-55007467 and JP-A-63172688 Official Gazettes proposethat there is set up a heat-resistible protecting layer composed of asilicone resin, an epoxy resin, a melamine resin, a phenol resin,fluorine resin, a polyimide resin, a polyamide resin or a celluloseresin at one surface of a substrate.

Further, JP-A-60201989 Official Gazette proposes that there is set up aheat-resistible protecting layer composed of an aromatic polyamide, andJP-A-60201989 Official Gazette proposes a heat-resistible protectinglayer composed of an aromatic polysulphone-based resin, respectively.However, the heat-resistible protecting layer is insufficient forprotecting the sticking phenomenon and, in the case that theheat-transferable recording medium is stored in a rolled state, there iscaused a so-called blocking phenomenon that the heat-resistibleprotecting layer adheres to a heat-transferable ink layer. By occurrenceof the blocking phenomenon, the heat-transferable recording medium in arolled state becomes not occasionally smoothly transferred, componentsin the ink layer which migrate and adhere to the heat-resistibleprotecting layer adhere to a heating body in the thermal head andsurroundings thereof, resulting in that printing quality is remarkablylowered.

Still further, JP-A-61143195 Official Gazette proposes that there is setup a back surface layer (a heat-resistible protecting layer) composed ofa silicone-graft or block acrylic-based copolymer. The back surfacelayer composed of the silicone-graft or block acrylic-based copolymer isexcellent in a slipping property and prevents a sticking phenomenon, andit is excellent in heat resistance and a blocking resistance. However,since the silicone-graft or block acrylic-based copolymer is poor in afilm formability, the back surface layer composed of the copolymer isshaved by the thermal head when continuously printing and, components ofthe back surface layer adhere to the heating body of the thermal headand circumstances thereof, printing quality lowers as well as in thecase of the occurrence of the blocking phenomenon.

For that reason, there is a drawback that the thermal head must be oftencleared in order to obtain an excellent printing quality.

JP-A-01221281 Official Gazette proposes that there is set up aheat-resistible protecting layer in which a silicone oil added to anethyl cellulose resin. However, as well as a method (JP-A-57129789Official Gazette) in which there is set up a resin layer in which thereis added a surface active agent which is solid or semi-solid at ordinarytemperatures, there is a drawback that additives such as the siliconeoil or the surface active agent migrate toward an ink layer, and thereare caused unevenness of transferring and lack of a picture image,resulting in that printing quality is remarkably lowered.

JP-A-01234292 Official Gazette describes that there is set up aheat-resistible protecting layer in which a silicone oil is added to acellulose ester resin containing acetate group or the ester resincontaining a silicone oil, and JP-A-07172076 Official Gazette describesthat there is set up a protecting layer in which waxes, higher fattyacid amides, or an ester are added to an acrylic resin, a polyesterresin, and a cellulose derivative, etc. However, there are stillremained an inconvenience such as the above-described stickingphenomenon and blocking phenomenon, and an inconvenience such as theunevenness of transferring and a lack of a picture image by migration ofthe additives toward the ink layer.

JP-A-06270561 Official Gazette proposes that there is employed acellulose modified polymer in which a cellulose and/or a cellulosederivative are a main polymer and a copolymer of a reactive silicone oilwith a vinyl monomer is a branch polymer as a protecting layer. As amethod for introducing the vinyl monomer into the cellulose derivative,two methods are proposed. One is a method in which a polymerization ofthe vinyl monomer is initiated by pulling out an active hydrogen of thecellulose, and another is a method in which vinyl groups are introducedinto the cellulose derivative, followed by allowing to polymerize withother vinyl monomers. Further, there are proposed two methods forintroducing a reactive silicone oil, and one is a method in which areactive silicone oil having vinyl group is allowed to react with othervinyl monomers and the above-described cellulose derivative.

Another is a method in which a reactive silicone oil having a hydroxylgroup or an epoxy group at a terminal is combined with an isocyanatecompound having vinyl group to introduce a double bond, followed byallowing to react with other vinyl monomers and the above-describedcellulose derivative. As described above, the method for the preparationof the cellulose-modified derivative is complicated in the JP-A-06270561Official Gazette and, productivity is poor, and the monomers to beemployed are expensive. Accordingly, the methods are not preferredbecause of a viewpoint of costs.

As described hereinabove, it is an existing circumstance that as theheat-resistible protecting layer for the heat-transferable recordingmedium, although there have been proposed various materials until now,there is occasionally caused a decline of a printing quality byoccurrence of a worse transferring and an abrasion of a thermal head, oroccurrence of a fracture, etc. in a substrate and, moreover, a blockingresistance and thermal head stain resistance, etc. are insufficient, andsatisfied protecting layers are not found out.

(The No. VII of the Present Invention)

Heretofore, as a method for coating a conductive coating, there has beenusually carried out a method in which a conductive coating compositionis coated on a nonconductive material to be coated such as inorganicmaterials and plastics, and after giving conductivity to the surface ofthe nonconductive material to be coated, and then, a finishing-coatingcomposition is coated by static coating.

As the conductive coating composition, there has been known, forexample, a mixture in which an amino alkyd-based resin and an aminoacrylic-based resin, etc. are mixed and dispersed with, for example,powdered metals such as a stainless steel, tin, copper, ad aluminum; ametal oxide such as zinc oxide, conductive fillers such as a titaniumdioxide-coated mica, a silicone, and cobalt sulphide, which are aconductive pigment.

However, since the powdered metals themselves have small electricresistance, although the use amount is small, those are not practicalbecause of a high price. Further, there is a drawback that since thosehave large specific gravity, those are separated from resin componentsand sink in a bottom of a vessel, and those aggregate, and those causehard-caking during a long term storage, it becomes difficult to disperseagain in an original state in spite of agitating, resulting in thatthere is formed a coating layer containing a small amount of powderedmetals, and conductivity becomes worse in a coating layer.

On the other hand, the metal oxides have a drawback that since the metaloxides themselves have a larger electric resistance compared to powderedmetals, in the case of intending to obtain a coating layer having equalconductivity to the powdered metals, use amount becomes large, resultingin that there become worse storage stability and physical properties ina coating composition.

Further, it is difficult to obtain a coating layer having an excellentconductivity by a small amount even in the conductive fillers.

Still further, it has been known that conductivity can be elevated byconductive pigments such as a conductive carbon and a scaly graphitewhich are a carbon-based pigment.

Although the conductive carbon is usually mixed and dispersed into acoating using a dispersing machine such as a ball mill or a sand mill,it has a drawback that when the conductive carbon is dispersed untilbecoming a state of primary particles in the case of dispersing,conductivity of the coating layer becomes poor by formation of a coatinglayer in which conductive carbon particles do not sufficiently bringinto contact each other, and in the case of increasing the mixing amountof the conductive carbon in order to elevate the conductivity, physicalproperties become poor in the coating layer. On the other hand, in thecase that aggregated particles of the conductive carbon are placed in alarge amount without sufficiently dispersing the particles of theconductive carbon, it has a drawback that a storage stability becomesworse in the coating composition, and an outer appearance of the coatinglayer also becomes poor after finishing.

Also, although the scaly graphite can form a coating layer having anexcellent conductivity even in the case of the smaller use amountcompared to the conductive carbon, it has a drawback that it is poor in,particularly, an adhering property to a plastic material to be coatedand adhesion to an over coating layer.

(The No. VIII of the Present Invention)

Heretofore, in the case of coating or repairing industrial machines,buildings, structures, furniture, and cars, etc., an acrylic urethanecoating has been mainly employed in view of durability, a finishingproperty, and weatherability.

The coating can form a coating layer having excellent properties as anordinary temperature-curable type one.

However, since the acrylic urethane coating is usually a two-liquidtype, it must be employed within a fixed time of period, resulting inthat it has a problem in coating workability. Further, in the coating,since a polyisocyanate compound having a relatively low molecular weightis employed as a curing agent, it includes a problem of toxicity and anirritating-property by vapor thereof when coating it at a coating site.

On the other hand, there have been conventionally proposed a variety ofmoisture-curable type coatings using isocyanate group which is a singleliquid type. For example, JP-A-56118409 and JP-A-64075578 OfficialGazettes disclose coatings using a copolymer containing isocyanategroup, whereby, an improvement is attained in view of coatingworkability and, safeness and public health.

However, the coatings do not attain to properties of the two liquid typeacrylic urethane coatings in view of dryability and physical propertieswhich are particularly desired as the ordinary temperature-curable typecoatings.

(The No. IX of the Present Invention)

In recent years, treatments of waste plastics are becoming a largesocial problem, and a biodegradable plastics has been largely paidattention. An aliphatic polyester is one of materials which are largelyexpected owing to a high biodegradability compared to other syntheticresin.

As the aliphatic polyesters which are industrially manufactured, therecan be enumerated, for example, a polylactic acid which is an aliphaticpolyester having a high melting point, a polyhydroxy butyrate, apolyglycol acid, and a polycaprolactone which is an aliphatic polyesterhaving a low melting point, etc.

The polylactic acid having a high molecular weight and thepolycaprolactone have been employed as medical uses such as surgicalstrings, medical gyps (JP-A-58081042 Official Gazette), and a face maskfor irradiating radiation rays (JP-A-60215018 Official Gazette), andcompost bags, fishing lines, tees for golfing and a variety of moldedarticles, and a hot-melt adhesive, etc., which are usual applications.

However, the aliphatic polyester having a high melting point, which istypified by by the polylactic acid (a melting point of approximately175° C.), the polyhydroxy butylate, and the polyglycol acid, etc., has adrawback of being hard and brittle because of high crystallinity andrigid molecular structure, and the polyester typified by thepolycaprolactone includes a practical problem because of a low meltingpoint.

Therefore, there have been conventionally investigated a method in whicha plasticizer is added to a polyester having a high melting point(JP-A-04335060 Official Gazette) and a mere copolymer of a polyesterhaving a high melting point with a polyester having a low melting point(JP-A-07053685 and JP-A-07316271 Official Gazettes), those are not stillsufficient from a viewpoint of practical uses.

That is, in the method in which the plasticizer is employed, therebecome largely problematic a toxicity and low biodegradability of theplasticizer itself, bleed out during molding, and staining of a mold,etc. In a lactide/E-caprolactone copolymer having a very long chainwhich is a completely block type as described in the JP-A-07316271Official Gazette, there is not almost improved a drawback of being hardand brittle, it is exceedingly limited in practical uses. Likewise, asdescribed in the JP-A-07053685 Official Gazette, in the case that themonomer formulation of the lactide/E-caprolactone is merely onlyregulated without any consideration of an average continuous chainlength of constructing monomer units, it is clear that there cannot bealways prepared a copolymer having a desired physical properties.

On the other hand, as a method for the preparation of alactide/E-caprolactone copolymer having a controlled average continuouschain, there is reported a method (Polymer Bulletin 25, 335-341 (1991),Macromol. Chem. 194, 907-912 (1993)) in which an average continuouschain length of respective units is controlled by changing reactiontemperature and catalysts. However, in the case of changing the reactiontemperature and catalysts, there are not avoidable fluctuations ofpreparation conditions and, in the case of consideration of a productionchange among several grades using an identical production apparatus, itis clear that it becomes a factor of a remarkable decline inproductivity.

Accordingly, it is virtually difficult that conventionally known methodsare applied to an actual production in an industrial fashion.

PROBLEM TO BE SOLVED BY THE INVENTION

A purpose of the No. I of the present invention is to obtain analiphatic polyester having a controlled thermal decomposition,hydrolizability, and biodegradability. Further, it is to modify aterminal of the aliphatic polyester without adversely affecting to otherphysical properties.

A purpose of the No. II of the present invention is to obtain aparticle-state composition for agriculture and gardening in which in thecase of coating it on a fertilizer, etc., biodegradability rate in athin layer can be appropriately controlled depending upon purposesthereof, a fertilizing duration period can be controlled and, afterelution of fertilizing components, the thin layer is disintegrated anddecomposed by microorganisms in soil without remaining in the soil, and,after a lapse of a cultivating period of farm products, the thin layerdisappears.

A purpose of the No. III of the present invention is to provide aparticle-state composition for agriculture and gardening in which in thecase of coating it on particle-state fertilizers, there can be employeda solvent which can be readily handled and is low in costs and, in thecase of coating it on fertilizers, etc., a fertilizing duration periodcan be controlled and, after elution of fertilizing components, a thinlayer is disintegrated and decomposed by microorganisms in soil withoutremaining in the soil, and, after a lapse of a cultivating period offarm products, residual components disappear by disintegration anddecomposition of the thin layer.

A purpose of the IV of the present invention is to provide an excellentmarking film in which there is solved a problem in relation to avolatilizing and migrating property of a plasticizer contained in acellulose ester.

A purpose of the No. V of the present invention is to provide aheat-sensitive transferable recording material having an excellentstrippability (a releasing property) in a formulation process of apicture image or thermally transferring in a thermally transferringmethod using a sublimatable dye, and the material can form a recordingpicture image having a high coloring concentration and an excellentclearness, and to provide a method for the preparation thereof.

A purpose of the No. VI of the present invention is to provide aheat-transferable recording material in which occurrence of a stickingphenomenon can be prevented and, even in the case that theheat-transferable recording material is stored in a rolled state at ahigh temperature for a long time of period, constructing components in aheat-resistible protecting layer do not migrate toward the surface of anink layer, and a blocking phenomenon does not occur and, theheat-resistible protecting layer is not shaved by an abrasion power of athermal head, whereby, an excellent printing quality can be obtained,and further, such the properties can be maintained even in the case ofapplying to a high speed printer.

A purpose of the No. VII of the present invention is to solve problemsin the above-described conventional conductive coating and, to provide aconductive coating composition having an excellent storage stabilitywhich can form a coating layer having an excellent adhesion to amaterial to be coated and a finishing coating layer, and an excellentconductivity.

A purpose of the No. VIII of the present invention is to provide amoisture-curable type graft copolymer which is useful for asingle-liquid type coating and a sealing agent which do not includetoxicity and an irritating problem, and which is excellent in dryabilityand does not deteriorate a variety of physical properties in a coatinglayer, and to provide a coating composition containing thereof.

A purpose of the No. IX of the present invention is to establish andprovide a lactide/e-caprolactone copolymer having more excellentphysical properties such as heat resistance and impact resistance, and anovel highly-effective method for the preparation in order tocommercially supply stably the copolymer by a low cost.

DISCLOSURE OF THE INVENTION

As a result of an investigation in relation to a structure of terminalgroups which is the purpose of the No. I in the present invention, thepresent inventors found out that an alcohol terminal (it means thepresence of a hydroxyl group at terminal) or a carboxylic acid terminal(it means the presence of a carboxylic group at terminal) affects to athermal decomposition property, hydrolizability, and biodegradability ina polymer chain obtained by a ring-opening polymerization of a cyclicester monomer, that the above-described various properties can becontrolled by decreasing the terminals, and that there can be obtained apreferred aliphatic polyester by modifying the terminals, particularly,by changing the polymer terminals to an alkyl group using an isocyanate,etc. after a ring-opening polymerization, and the present invention hasbeen completed.

That is, No. 1 of the present invention provides an aliphatic polyester,which is an aliphatic polyester composed of at least one kind of amonomer unit of any one of a lactone or a lactide, in which a proportionof the number of the alcohol terminals is not more than 50% based on thenumber of total terminals in the aliphatic polyester and/or a proportionof the number of the carboxylic acid terminals is not more than 30%based on the number of total terminals in the aliphatic polyester.

No. 2 of the present invention provides an aliphatic polyester describedin the No. 1 of the present invention in which a proportion of thenumber of the alkyl group terminals and/or alkenyl group terminals(herein, the alkyl group and/or alkenyl group are a group having astraight chain and cyclic or branched chain which contain a carbonnumber of 1-24 pieces) is not less than 30% based on the total terminalsin the aliphatic polyester.

No. 3 of the present invention provides an aliphatic polyester describedin any one of the No. 1 or 2 of the present invention in which there iscontained a bond produced by allowing to react a modifying agent withthe alcohol terminals and/or carboxylic acid terminals in 0.2-40 pieceson average based on one molecule of a polymer after modifying.

No. 4 of the present invention provides an aliphatic polyester describedin No. 4 of the present invention in which the bond produced by allowingto react the modifying agent is at least one selected from the groupconsisting of urethane bond, ether bond, ester bond, and amide bond.

No. 5 of the present invention provides a method for the preparation ofan aliphatic polyester by adjusting a proportion of the number of thealcohol terminals to not more than 50% and/or a proportion of the numberof the carboxylic acid terminals to not more than 30% based on thenumber of total terminals, in which at least one kind of a lacton orlactide is polymerized by ring-opening using at least one kind of amonoalcohol having a high boiling point or a metal alkoxide as aninitiator.

No. 6 of the present invention provides a method for the preparation ofan aliphatic polyester described in the No. 5 of the present inventionin which a bond produced by allowing to react a modifier to terminals inthe aliphatic polyester having the alcohol terminals and/or thecarboxylic acid terminals is contained in 0.2-40 pieces on average.

In relation to the purpose of the No. II of the present invention, as aresult of an intensive investigation concerning a selection of amaterial for a thin layer in order to prepare a particle-statefertilizer coated by a degradable thin layer having degradability inwhich duration period of a fertilizing effect can be widely controlled,the present inventors found out that a terminal-controlled aliphaticpolyester is appropriate as a coating layer for agradually-dischargeable fertilizer, and the present invention has beencompleted.

That is, No. 7 of the present invention provides a particle-statecomposition for agriculture and gardening characterized in that surfaceof a particle-state fertilizer is coated by a coating material II-Aalone or a mixture of the coating material II-A with a coating materialII-B, the coating material II-A is composed of a terminal-controlledaliphatic polyester, the terminal-controlled aliphatic polyester is analiphatic polyester composed of at least one kind of monomer units ofany one of a lactone or a lactide, and in which a proportion of thenumber of the alcohol terminals is not more than 50% based on the numberof total terminals in the aliphatic polyester and/or a proportion of thenumber of the carboxylic acid terminals is not more than 30% based onthe number of total terminals in the aliphatic polyester, the coatingmaterial II-B is composed of at least one kind of selected from thegroup consisting of an olefine polymer, a copolymer containing anolefine, a vinylidene chloride polymer, a copolymer containingvinylidene chloride, a diene-based polymer, waxes, a petroleum resin, anatural resin, a cellulose acetate resin, a polycaprolactone, oils &fats and a modified product therefrom.

No. 8 of the present invention provides a particle-state composition foragriculture and gardening described in the No. 7 of the presentinvention, in which a proportion of the number of the alkyl groupterminals and/or alkenyl group terminals (herein, the alkyl group and/oralkenyl group is a group having a straight chain and cyclic or branchedchain which contain a carbon number of 1-24 pieces) is not less than 30%based on the total terminals in the aliphatic polyester.

No. 9 of the present invention provides a particle-state composition foragriculture and gardening described in any one of the No. 7 or 8 of thepresent invention, in which the terminal-controlled aliphatic polyesteris an aliphatic polyester obtained by allowing to react a modifier withthe alcohol terminals and/or the carboxylic acid terminals in analiphatic polyester composed of at least one kind of monomer units of alactone or a lactide, and bonds produced by allowing to react themodifier are contained in 0.2-40 pieces on average based on one moleculeof a polymer after modifying.

No. 10 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 9 of the presentinvention, in which the bonds produced by allowing to react the modifieris at least one kind selected from the group consisting of a urethanebond, an ether bond, an ester bond, and an amide bond.

No. 11 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 7 of the presentinvention, in which the coating material II-B is a polycaprolactone, acellulose acetate, or a mixture thereof.

No. 12 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 7 or 11 of thepresent invention, in which there are further added inorganic fillersand/or additives for resins.

No. 13 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 12 of the presentinvention, in which the inorganic fillers are talc, calcium carbonate,or a mixture thereof.

In relation to the purpose of the No. III of the present invention, as aresult of an intensive investigation concerning a selection of a coatingmaterial having degradability in order to prepare a particle-statefertilizer coated by a degradable thin layer in which a duration periodof a fertilizing effect can be controlled, and, in consideration ofsolubility into a solvent in coating and price of the solvent, thepresent inventors have completed the present invention.

That is, No. 14 of the present invention provides a particle-statecomposition for agriculture and gardening characterized in that thesurface of a particle-state fertilizer is coated by a coating materialII-A alone or a mixture of the coating material II-A with a coatingmaterial II-B, the coating material II-A is composed of a cyclicester-modified cellulose ester, the coating material II-B is composed ofof at least one kind of selected from the group consisting of an olefinepolymer, a copolymer containing an olefine, a vinylidene chloridepolymer, a copolymer containing vinylidene chloride, a diene-basedpolymer, waxes, a petroleum resin, a natural resin, a cellulose acetateresin, a polycaprolactone, oils & fats and a modified product therefrom.

No. 15 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 14 of the presentinvention, in which the cyclic ester-modified cellulose ester is acellulose ester derivative obtained by a ring opening graftpolymerization of a cyclic ester with a cellulose ester having hydroxylgroups.

No. 16 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 15 of the presentinvention, in which the cellulose ester having hydroxyl groups is acellulose acetate, a cellulose acetate-butylate, a celluloseacetate-propionate, or a mixture thereof. No. 17 of the presentinvention provides a particle-state composition for agriculture andgardening described in the No. 15 of the present invention, in which thecyclic ester is ε-caprolactone.

No. 18 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 14 of the presentinvention, in which the coating material II-B is a polycaprolactone, acellulose acetate, or a mixture thereof.

No. 19 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 14 the presentinvention, in which inorganic fillers and/or additives for resins arefurther added.

No. 20 of the present invention provides a particle-state compositionfor agriculture and gardening described in the No. 19 of the presentinvention, in which the inorganic fillers are talc, calcium carbonate,or a mixture thereof.

In relation to the purpose of the No. IV of the present invention, as aresult of an intensive investigation in view of the above-describedcircumstances, the present inventors found out that a cellulose esterderivative of a fatty acid is excellent in a nonvolatility andnonmigrating property, and it is appropriate for a marking film, andwhich is obtained by a ring-opening graft polymerization of cyclicesters to a fatty acid cellulose ester having hydroxyl groups, and thepresent invention has been completed.

That is, No. 21 of the present invention provides a base film for amarking film characterized by comprising a resin primarily containing acellulose ester derivative of a fatty acid obtained by a ring-openinggraft polymerization of cyclic esters to a fatty acid cellulose esterhaving hydroxyl groups.

No. 22 of the present invention provides a base film for a marking filmdescribed in the No. 21 of the present invention, in which the fattyacid cellulose ester having hydroxyl groups is at least one kindselected from the group consisting of a cellulose acetate, a celluloseacetate-butylate, and a cellulose acetate-propionate.

No. 23 of the present invention provides a base film for a marking filmdescribed in the No. 21 or 22 of the present invention, in which thefatty acid cellulose ester having hydroxyl groups is a cellulose acetatehaving a substitution degree of acetyl groups of 1-3.

No. 24 of the present invention provides a base film for a marking filmdescribed in any one of the Nos. 21-23 of the present invention, inwhich the cyclic ester are ε-caprolactone.

No. 25 of the present invention provides a base film for a marking filmdescribed in any one of the Nos. 21-24 of the present invention, inwhich ε-caprolactone is graft-polymerized in 2-50 mol based on glucoseunit in the fatty acid cellulose ester having hydroxyl groups.

No. 26 of the present invention provides a base film for a marking filmdescribed in any one of the Nos. 21-25 of the present invention, inwhich a mass average molecular weight (heretofore, it has been referredto as a weight average molecular weight, hereinafter the same) is200,000-2,000,000 in the fatty acid cellulose ester derivative.

As a result of an intensive investigation in order to attain the purposeof the No. V in the present invention, the present inventors found outthat there can be obtained a picture image recording material having anexcellent strippability from a heat transfer sheet and a highconcentration of color generation, and a recording picture image havingan excellent clearness can be formed on the picture image recordingmaterial by forming a dye receiving layer in a picture image recordingmaterial for a heat-sensitive transfer using a cyclic ester-modifiedcellulose derivative.

That is, No. 27 of the present invention provides a picture imagerecording material for a heat-sensitive transfer recording is composedof a cyclic ester-modified cellulose derivative obtained by aring-opening polymerization of a cyclic ester to a cellulose esterderivative having hydroxyl groups.

No. 28 of the present invention provides a picture image recordingmaterial for a heat-sensitive transfer recording described in any one ofthe No. 27 of the present invention, in which a dye receiving layer iscoated on at least one surface of a base material.

Further, Nos. 29 and 30 of the present invention provide a picture imagerecording material for a heat-sensitive transfer recording described inany one of the No. 27 of the present invention, in which the cellulosederivative having hydroxyl groups is a cellulose acetate, and the cyclicester is ε-caprolactone.

No. 31 of the present invention provides a method for the preparation ofa picture image recording material for a heat-sensitive transferrecording by coating a solution of a cyclic ester-modified cellulosederivative obtained by a ring-opening polymerization of a cyclic esterwith a cellulose derivative having hydroxyl groups.

As a result of a variety of investigations in order to attain a purposeof the No. VI in the present invention, the present inventors found outthat a specified cellulose derivative is desirable as a heat-resistiblerecording layer for a heat transfer recording material, and the presentinvention has been completed.

That is, No. 32 of the present invention provides a heat-transferrecording medium which comprises setting up a heat-transfer ink layer onthe surface of a supporting material, and setting up a heat-resistibleprotecting layer on other surface of the supporting material, and inwhich the heat-resistible protecting layer is composed of a cyclicester-modified cellulose derivative obtained by a ring-openinggraft-polymerization of a cyclic ester to a cellulose derivative havinghydroxyl groups.

Further, No. 33 of the present invention provide a heat-transferrecording medium described in the No. 32 of the present invention, inwhich the cellulose derivative having hydroxyl groups is a celluloseacetate, and No. 34 of the present invention provide a heat-transferrecording medium described in the No. 32 of the present invention, inwhich the cyclic ester is ε-caprolactone.

As a result of an intensive investigation in order to attain a purposeof No. VII the present invention and to solve the above-describedproblems, the present inventors found out that a coating composition isexcellent in storage stability and, further can form a coating layerwhich is excellent in adhesion to an article to be coated and a coatinglayer of a finishing coating and conductivity, and the coatingcomposition contains a resin primarily containing a cellulose esterderivative obtained by a ring-opening graft-polymerization of a cyclicester to a cellulose derivative having hydroxyl groups and a conductivepigment in which a specified proportion of a conductive carbon black isemployed together a scaly graphite, and the present invention has beencompleted.

No. 35 of the present invention provide a conductive coating compositionwhich comprises formulating 75-85% by mass of a conductive coating resin(A) composed of 2-20% by mass of a cellulose ester derivative (a)obtained by a ring-opening graft-polymerization of a cyclic ester to acellulose derivative having hydroxyl groups and 98-80% by mass of aresin for coating (b) [total of (a) and (b) is 100% by mass] and 25-15%by mass of a conductive pigment (B) [total of (A) and (B) is 100% bymass] composed of 40-60% by mass of a conductive carbon black (c) and60-40% by mass of a scaly graphite (d) [total of (c) and (d) is 100% bymass].

No. 36 of the present invention provide a conductive coating compositiondescribed in the No. 35 of the present invention, in which the celluloseester having hydroxyl groups is at least one kind selected from thegroup consisting of a cellulose acetate, a cellulose acetate-butylate, acellulose acetate-propionate, and a cellulose acetate-nitrate.

No. 37 of the present invention provide a conductive coating compositiondescribed in the No. 35 or 36 of the present invention, in which thecellulose ester having hydroxyl groups is a cellulose acetate having anacetyl group substitution degree of 1-2.9. No. 38 of the presentinvention provide a conductive coating composition described in any oneof the Nos. 35-37 of the present invention, in which the cyclic ester isε-caprolactone.

No. 39 of the present invention provide a conductive coating compositiondescribed in any one of the Nos. 35-38 of the present invention, inwhich the cellulose ester (a) contains 1-50 mol of graft-polymerizedε-caprolactone based on a glucose unit in the cellulose ester havinghydroxyl groups.

No. 40 of the present invention provide a conductive coating compositiondescribed in any one of the Nos. 35-39 of the present invention, inwhich a mass average molecular weight is 50,000-1,000,000 in thecellulose ester derivative (a).

As a result of an intensive investigation in order to attain a purposeof No. VIII in the present invention and to solve the above-describedproblems, the present inventors found out that the above-describedproblems can be solved by using a cellulose ester derivative obtained bya ring-opening graft-polymerization of a cyclic ester to a cellulosederivative having hydroxyl groups and a graft polymer in which anisocyanate group component is introduced into a main chain of a graftcopolymer obtained by copolymerization of polymerizable unsaturatedmonomers as a compound of a coating thin layer, and optionally byformulating a curing agent and resin components, and the presentinvention has been completed.

That is, No. 41 of the present invention provides a graft copolymer (I)characterized in that the graft copolymer (I) is obtained bycopolymerization of 1-30% by mass of a cellulose ester derivative (a)obtained by a ring-opening graft-polymerization of a cyclic ester to acellulose derivative having hydroxyl groups with 70-99% by mass of apolymerizable unsaturated monomer (b) [total of (a) and (b) is 100% bymass], and introduction of an isocyanate group component into the graftcopolymer is conducted by the use (i) of an isocyanate group-containedunsaturated monomer (f) as a portion of the polymerizable unsaturatedmonomer (b), or the reaction (ii) of the polyisocyanate compound (c) toan active hydrogen-contained polymerizable monomer (h) which is employedas a portion of the polymerizable unsaturated monomer (b) [in the case,total of (b) and (c) correspond to the above-described 70-99% by mass(b), and isocyanate group content is 0.5-28.5% by mass in the graftcopolymer (I).].

No. 42 of the present invention provides a graft copolymer described inthe No. 41 of the present invention characterized in that mass averagemolecular weight is 2,000-150,000.

No. 43 of the present invention provides a graft copolymer described inthe No. 41 of the present invention characterized in that a glasstransition temperature is 0-90° C.

No. 44 of the present invention provides a coating composition whichcontains a graft copolymer (I) described in the No. 41 or 42 of thepresent invention and, optionally, at least one kind of componentsdescribed below;

-   -   a polyisocyanate compound (II),    -   a cellulose ester derivative (III),    -   a modified vinyl-based copolymer (III′) not containing an        isocyanate group component which comprises copolymerization of        5-75% by mass of the cellulose ester derivative (III) with        25-95% by mass of other polymerizable unsaturated monomer (g)        (total of (III) and (g) is 100% by mass),    -   a graft copolymer (IV) which comprises copolymerization of 3-30%        by mass of a macromonomer (m) with 70-97% by mass of other        polymerizable unsaturated monomer (J) (it is the component (b)        except the component (h)) (total of (m) and (j) is 100% by        mass), and,    -   a nonaqueous dispersed resin (V),        in which the graft copolymer (I) is contained in not less than        50% by mass in the total resin solid components which are        composed of the (I), (II), (III), (III′), (IV), and (V) which        are 100% by mass.

No. 45 of the present invention provides a coating composition describedin the No. 44 of the present invention, in which the polyisocyanatecompound (II) is contained in 0.5-40% by mass based on the total resinsolid components.

No. 46 of the present invention provides a coating composition describedin the No. 45 of the present invention, in which the polyisocyanatecompound (II) is a polymer (e) containing a low molecular weightcompound (d) having at least two isocyanate groups in the molecule or anunsaturated monomer (f) having an isocyanate group.

No. 47 of the present invention provides a coating composition describedin any one of the Nos. 44-46 of the present invention, in which thecellulose ester derivative (III) is contained in 0.5-20% by mass basedon total resin solid components.

No. 48 of the present invention provides a coating composition describedin any one of the Nos. 44-47 of the present invention, in which themodified vinyl-based copolymer (III′) is contained in 1-30% by massbased on total resin solid components.

No. 49 of the present invention provides a coating composition describedin any one of the Nos. 44-48 of the present invention, in which thegraft copolymer (IV) is contained in 1-20% by mass based on total resinsolid components.

No. 50 of the present invention provides a coating composition describedin any one of the Nos. 44-49 of the present invention, in which anonaqueous dispersed resin (V) (resin components) is contained in0.5-50% by mass based on total resin solid components.

No. 51 of the present invention provides a coating composition describedin any one of the Nos. 50 of the present invention, in which thenonaqueous-dispersed resin (V) is resinous components in a dispersedliquid of polymer particles (q) having a glass transition temperature of0-100° C. obtained by polymerization of a polymerizable unsaturatedmonomer (g) in a nonaqueous solvent-under the presence of a dispersantwhich is a polymer (p) having a mass average molecular weight of3,000-150,000.

As a result of a variety of investigations in order to attain a purposeof No. IX the present invention, the present inventors found out asynthesis method by which an average continuous chain length can befreely controlled in a copolymer, and that the method is an influentialmethod for giving a new physical property to a lactic acidpolymer/copolymer, and the present invention has been completed.

That is, No. 52 of the present invention provides a lactide/lactonecopolymer in which an average continuous chain length is at least 3 in alactide unit and an average continuous chain length is 1-10 in a lactoneunit, and in which the lactide unit is composed of a random portionhaving the average continuous chain length of not more than 5 and ablock portion having the average continuous chain length of not lessthan 5, and a number average continuous chain length 1LL(B) in the blockportion is satisfied by formula described below;1LL(B)²>(fL/(fL+fCap))³×23(wherein, fL is a lactone component in the lactide/lactone copolymer andfCap is a lactide component in the lactide/lactone copolymer).

No. 53 of the present invention provides a method for the preparation ofa lactide/lactone copolymer having an average continuous chain length ofnot less than 3 in the lactide unit and an average continuous chainlength of 1-10 in the lactone unit or the lactide/lactone copolymershown in the No. 52 of the present invention, characterized in that apolymerization is conducted by adding residual lactide during or after apolymerization of 2-85% of the lactide in total lactide components withthe lactone.

No. 54 of the present invention provides a method for the preparation ofa lactide/lactone copolymer having an average continuous chain length ofnot less than 3 in the lactide unit and an average continuous chainlength of 1-10 in the lactone unit or a lactide/lactone copolymer havingan average continuous chain length of 1-20 in the lactide unit and anaverage continuous chain length of not less than 3 in the lactone unit,or a lactide/lactone copolymer shown in the No. 52 of the presentinvention, characterized in that a polymerization is conducted by addingresidual lactide and lactone during or after a polymerization of 2-85%of the lactide in total lactide components with 50-98% of the lactone intotal lactone components.

No. 55 of the present invention provides a method for the preparation ofa lactide/lactone copolymer having an average continuous chain length ofnot less than 3 in the lactide unit and an average continuous chainlength of 1-10 in the lactone unit or a lactide/lactone copolymer havingan average continuous chain length of 1-20 in the lactide unit and anaverage continuous chain length of not less than 3 in the lactone unit,or a lactide/lactone copolymer shown in the No. 52 of the presentinvention, characterized in that there is repeatedly conducted anoperation by adjusting the ratio of a lactide/lactone unit number to notmore than 2.5 and adding at least one of residual lactide and lactoneduring or after a polymerization of 2-85% of the lactide in totallactide components with 50-98% of the lactone in total lactonecomponents.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1-6 represent a graph showing results of Table I-1 in the No. I ofthe present invention.

FIG. 7 is an outlined drawing showing one example of an apparatus whichis appropriate for the preparation of an article of the No. II of thepresent invention.

FIG. 8 is a ¹³C-NMR chart of a reaction product after on of the step 1in Example IX-3.

FIG. 9 is a ¹³C-NMR chart of a reaction product after on of the step 2in Example IX-3.

Brief Explanation of Marks in the FIG. 7

-   -   1 Spraying tower    -   2 Throwing inlet for a fertilizer    -   3 Outlet for blowing waste gas    -   4 Nozzle for a fluid    -   5 Pump    -   6 Valve    -   7 Outlet for discharging    -   8 Heat exchanger    -   9 Orifice flow meter    -   10 Blower    -   11 Liquid tank    -   T₁, T₂, T₃ Thermometer    -   SL Steam

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be illustrated in detail.

First of all, the No. I of the invention is illustrated.

As the cyclic ester monomer to be employed in the present invention, alactone and lactide, etc. are enumerated.

The lactone is a compound having an intramolecular cyclic esterstructure and, specifically, there can be exemplified lactones such asβ-propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactone,γ-varelolactone, β-varelolactone, α,α-dimethyl-p-propiolactone,β-ethyl-β-varelolactone, α-methyl lactone, β-methyl-ε-caprolactone,γ-methyl-ε-caprolactone, 3,3,5-trimethyl-ε-caprolactone,3,5,5-trimethyl-ε-caprolactone, enantolactone, and dodecalactone.

Further, the lactide to be described in the present invention is abimolecular cyclic ester of an aliphatic hydroxycarboxylic acid and,specifically, there can be exemplified glycolide, lactide, diethylglycolide, dimethyl glycolide, α,α-dimethyl glycolide, L-lactide,D-lactide, D,L-lactide and MESO-lactide, etc. which are the bimolecularcyclic ester of lactic acid, glycol acid, ethyl glycol acid, dimethylglycol acid, etc.

In the present invention, the above-described cyclic ester monomers canbe employed solely or in combination of two or more kinds.

In the present invention, in the case of ring-opening polymerization ofthe above-described cyclic ester monomers, there are preferably employedthe cyclic ester monomers having water content of not more than 80 ppmand an acid value of not more than 0.12 mg(KOH)/g. In the case of amonomer having the water content and the acid value exceeding the abovevalues, it is difficult to adjust a carboxylic terminal of a polymer tonot more than 30% because of an action as an initiator for ring-openingby water and an acid (hydroxyl acid). Further, it becomes difficult toallow to completely react even in capping of carboxylic acid or alcoholterminals, and it is incapable of attaining the purpose of the presentinvention.

In the present invention, in the case of ring-opening polymerization ofthe above-described cyclic ester monomers, a monoalcohol and/or a metalalkoxide are employed as a polymerization initiator.

When the lactone and lactide are ring-opening-polymerized by employingthe monoalcohol as a polymerization initiator, an initiating terminalbecomes a monoalkyl group, and a polymerized terminal becomes hydroxylgroup. In the present invention, an alkyl terminal represents an alkylgroup from the above-described monoalcohol.

For example, when ε-caprolactone is polymerized using ROH (R representsan alkyl group) as an initiator, there is obtained a polymer having aformula described below.RO(CO(CH₂)₅O)_(n)H

Accordingly, although proportion of the number of the alcohol terminalbecomes 50% with respect to the number of total terminals, when water iseliminated from the alcohol terminal, the proportion of the number ofthe alcohol terminal becomes not more than 50%.

On the other hand, when the lactone and lactide arering-opening-polymerized using the metal alkoxide as a polymerizationinitiator, an initiating terminal becomes a monoalkyl group, and aterminal of a polymer becomes a metal, and it becomes hydroxyl group bysubjecting to hydrolysis. In the present invention, an alkyl terminalrepresents an alkyl group from the above-described metal alkoxide.

For example, when ε-caprolactone is polymerized using M(OR)_(m) (Mrepresents a metal, and R represents an alkyl group) as an initiator,there is obtained a polymer having a formula described below.(RO(CO(CH₂)₅O)_(n))_(m)M

Metal terminal becomes an alcohol terminal by a post treatment such asneutralization and hydrolysis after polymerization.

The monoalcohol to be employed is mono-ols having a carbon number of1-24, preferably, mono-ols having a high boiling point of not less than150° C. For example, there can be employed hexane, heptane, octane,butoxyethanol, phenol, ethoxyphenol, cyclohexanol, an alcohol having analkenyl group such as hydroxyethyl acrylate, a reaction product of analcohol with a lactone, a reaction product of an alcohol with a cyclicether (for example, ethylene oxide and propylene oxide, butylene oxide,and styrene oxide, etc.), or a compound having one hydroxyl group atmost. It is to be noted that the compound having one hydroxyl group atmost is a product obtained by a ring opening polymerization of a lactoneor lactide using a metal alkoxide which is an initiator and, a terminalof a polymer is a metal, and it becomes a hydroxyl group by hydrolysis,in which hydrolysis degree is low, and hydroxyl group is not more than1.

The initiators may be employed solely or even in combination of two ormore kinds.

In the case that the initiators are employed, a catalyst becomesrequired. As the catalyst, there are enumerated metal compounds such asAl, Ti, Sn, and Zn which are usually employed, and it is not limited tothe compounds. The compounds may be employed solely or even incombination of two or more kinds.

As the metal alkoxide to be employed as an initiator in the presentinvention, specifically, there are enumerated aluminum alkoxide,titanium alkoxide, zinc alkoxide, tin alkoxide, zirconium alkoxide,yttrium alkoxide, samarium alkoxide, niobium alkoxide, neodymiumalkoxide, and antimony alkoxide, etc.

As the alkoxide, there are enumerated aliphatic or aromatic alkoxideshaving a carbon number of 1-24 such as a methoxide, an ethoxide, apropoxide, a butoxide, a phenoxide, and 2,6-diisopropyl phenoxide.

The alkoxides may be employed solely or even in combination of two ormore kinds.

As a compound for giving urethane bond, ether bond, ester bond, andamide bond to the aliphatic polyester of the present invention, thereare enumerated an isocyanate compound such as a monoisocyanate, adiisocyanate, and a triisocyanate, a carbodiimide compound, anisocyanurate compound, a Schiff base, an anhydride such as succinicanhydride, a cyclic ether such as ethylene oxide, propylene oxide,butylene oxide, and an epoxide such as styrene oxide.

At least one kind of the compounds are preferably and, for example, thecyclic ether and the isocyanate are preferably employed together. Morepreferably, the epoxide is desirably added after the completion of areaction by adding the isocyanate.

For example, by adding 1/2 molar ratio of the diisocyanate to amonofunctional alcohol-terminated aliphatic polyester obtained using amonoalcohol which is an initiator, an aliphatic polyester having alkylgroups at terminals is obtained by connecting through a urethane bondderived from 2 mols of the aliphatic polyesters.

Further, by adding an epoxy compound such as butylene oxide, an alcoholterminal is produced together with formation of an ester bond in acarboxylic acid terminal, and an alcohol terminal is produced togetherwith formation of an ether bond in an alcohol terminal. Accordingly, bya reaction of the alcohol terminals with an isocyanate, there isobtained an aliphatic polyester having an alkyl terminal at bothterminals as well as the above description.

In the case, there becomes smaller a proportion occupied by the alcoholterminal and the carboxylic acid terminal with respect to totalterminals in the aliphatic polyesters, and there becomes larger aneffect for a thermal degradability, hydrolizability, andbiodegradability.

Further, the urethane bond, ether bond, ester bond, or amide bond may beeven remained at terminals of a polymer molecule, and a monoepoxycompound and monoisocyanate compound, etc. are employed for capping theterminals of a polymer chain produced and, a polyfunctional compoundsuch as a diepoxy compound and diisocyanate compound is employed forcoupling a polymer chain produced.

The present invention also includes a polymer obtained by allowing toreact a diisocyanate with both terminals of a diol-initiated aliphaticpolyester and allowing to connect a mono-ol-initiated aliphaticpolyester to residual isocyanate groups.

In the present invention, an aliphatic polyester which is excellent inthermal disintegrabability, hydrolizability, and biodegradability can beobtained by the above-mentioned synthesis methods, and the presentinvention is not limited to those.

Proportion of the alcohol terminals and carboxylic acid terminals is notmore than 50% and not more than 30%, preferably not more than 20% andnot more than 8%, and more preferably 0% and 0%, respectively, withrespect to total terminals of the aliphatic polyester, by which therecan be controlled thermal disintegrabability, hydrolizability, andbiodegradability.

In the case that it has the alcohol terminals and carboxylic acidterminals exceeding the above-described range (50%), thermaldegradability, hydrolizability, and biodegradability become an identicalextent to those obtained by a prior art, resulting in that the purposeof the present invention cannot be attained.

In the present invention, it is desired to possess an alkyl groupterminal and/or an alkenyl group terminal of not less than 30% withrespect to total terminals, which have a straight chain, a ring, and abranch containing 1-24 carbons.

In the case that the carbon number in the alkyl group and/or the alkenylgroup exceeds 24, it affects to various physical properties of thealiphatic polyester, resulting in that the purpose of the presentinvention cannot be attained.

Further, in the case that the alkyl group terminal and/or the alkenylgroup terminal are not more than 30%, it becomes difficult to controlthe thermal degradability, hydrolizability, and biodegradability.

It is to be noted that the alkyl group terminal in the present inventionis derived from a monoalcohol which is an initiator, and derived from amodifier to be employed for capping the hydroxyl terminals andcarboxylic acid terminals. Further, the alkenyl group terminal isderived from alcohol terminals by elimination of water, or derived fromhydroxyethyl(meth)acrylate employed as an initiator and a modifier.

In the present invention, the aliphatic polyester may even have 0.2-40pieces of bonds other than ester bonds in one polymer molecule. That is,one polymer molecule after modifying has 0.2-40 pieces (on average) ofbonds produced by modifying the alcohol terminals and/or carboxylic acidterminals through allowing to react a modifier with the aliphaticpolyester.

For example, if an alcohol-terminated polycaprolactone produced bypolymerization of caprolactone using octanol which is an initiator isallowed to react with ½ equivalent of a diisocyanate, since twomolecules of the polycaprolactone connect to each other through twourethane bonds, one molecular chain of a polymer after modifying resultsin containing two urethane bonds.

The bonds are produced by controlling the terminals of a polymer chain,and the polymer is preferably controlled in a polymerization degree of0.2-2% {(number of bond produced by modifying)/(polymerization degree ofa lactone or lactide monomer)×100}. The bonds other than ester bonds,that is, in the case that the bonds produced by bonding to the modifierare too large amount than the above-described range, it affects tovarious physical properties of the aliphatic polyester, resulting inthat the purpose of the present invention cannot be attained.

In the present invention, solvents can be employed in the case of thering-opening polymerization of the cyclic ester monomer. The solvents tobe employed herein are not particularly limited if those are a compoundwhich does not react with catalysts, initiators, and monomers. As thepreferred solvents, there are enumerated an aromatic hydrocarbon such astoluene and xylene, and an aliphatic hydrocarbon such as hexane andcyclohexane. Further, in the present invention, the aliphatic polyestercan be also prepared without using solvents in the case of thering-opening polymerization of the cyclic ester monomer.

In the present invention, the cyclic ester monomer can be polymerized byring-opening through continuously supplying the cyclic ester monomerinto a continuous polymerization apparatus.

As the continuous polymerization apparatus to be employed, there can beemployed a vessel type reactor equipped with an agitator, a plug-flowtype reactor, and a combination thereof.

More specifically, in addition to the vessel type reactor equipped withan agitator, there can be employed a static mixer type reactor, a columntype reactor, and an extruder type reactor, etc. Further, the reactorscan be employed in combination of two or more kinds.

Hereinafter, the No. II of the present invention will be illustrated.

The particle-state composition for agriculture and gardening of thepresent invention is a particle-state fertilizer characterized by beingobtained spraying a solution composed of the above-described coatingmaterials on the particle-state fertilizer and, by coating whilesimultaneously drying through blowing a high speed hot air stream tomomentarily dry, and in which a coating layer has degradability anddisintegrability, and a duration period of a fertilizing effect can becontrolled.

In the beginning, a terminal-controlled aliphatic polyester isillustrated which is employed as a coating material II-A in the presentinvention.

As the terminal-controlled aliphatic polyester in the present invention,there is employed the aliphatic polyester of the No. I of the presentinvention.

Materials employed as a coating material II-B in the present inventioninclude at least one or more kinds of substances selected from the groupconsisting of an olefine polymer, a copolymer containing an olefine, avinylidene chloride polymer, a copolymer containing vinylidene chloride,a diene-based polymer, waxes, a petroleum resin, a natural resin, acellulose acetate resin, a polycaprolactone, oils & fats and a modifiedproduct thereof.

The olefine polymer includes a polyethylene, a polypropylene, anethylene-propylene copolymer, a polybutene, a butene-ethylene copolymer,a butene-propylene copolymer, and a polystyrene, etc., the copolymercontaining an olefine include an ethylene-vinyl acetate copolymer, anethylene-acrylic acid copolymer, an ethylene-acrylate copolymer, anethylene-methacrylate copolymer, an ethylene-carbon monoxide copolymer,and an ethylene-vinyl acetate-carbon monoxide copolymer, etc. Thecopolymer containing vinylidene chloride includes a vinylidenechloride-vinyl chloride based copolymer, and the diene-based polymerincludes a butadiene polymer, an isoprene polymer, a chloroprenepolymer, a butadiene-styrene copolymer, an EPDM polymer, and astyrene-isoprene copolymer, etc. The waxes include bee waxes, woodwaxes, and paraffins, etc., and the natural resin includes a naturalrubber and rosins, etc. The cellulose acetate resin includes diacetateshaving an average substituent degree of 2.5 and triacetates having anaverage substitution degree of 2.9. The polycaprolactone is a polyesterprepared by a ring-opening addition polymerization of ε-caprolactone,and which has a molecular weight of not less than 10,000, and preferably50,000-100,000. The oils & fats and the modified product thereof are ahydrogenated oil, a solid fatty acid, and metal salts thereof, etc.

Weight percentage of the coating material with respect to a coatedparticle-state substance (for example, a particle-state fertilizer) inthe present invention, that is, coating ratio ranges preferably in 2-20%(by mass). Further, the coating material II-A is employed in a range of10-100% (by mass) based on total of the coating material II-A and thecoating material II-B, and preferably in a range of 50-100% (by mass),and the coating material II-B is employed in a range of 0-90% (by mass),and preferably in a range of 0-50% (by mass).

It is to be noted that the coating material in the present invention canbe optionally mixed with third coating layer components which arecapable of being mixed. As such the third coating layer components (itis shown as coating material II-C in Table II-1 of Examples), there areenumerated additives for resins such as plasticizers, surface activeagents as an elution controller, talc as insoluble fillers, calciumcarbonate, and fillers such as metal oxides, etc. Mixture is required tobe uniformly mixed. In the case of not being uniform, micro particlesare partially one-sided and a continuous phase is lost in the coatingmaterials, resulting in that an effect by the coating material is lost.

Addition amount of the fillers which include talc, calcium carbonate,metal oxides, and a mixture thereof is 0-200 parts by weight, preferably10-150 parts by weight, and more preferably 20-100 parts by weight basedon 100 parts by weight of the coating material II-A alone or 100 partsby weight of the mixture of the coating material II-A with the coatingmaterial. II-B. In the case of larger than the range, holes are apt tobe formed in a coating thin layer, and an elution of the fertilizercannot become controlled.

In the present invention, a fourth component is further optionallyemployed for the coating thin layer. As the fourth component, forexample, there can be enumerated a photo-degradation accelerator, abiodegradation accelerator, an elution controller, and cellulose powder,etc., and the components can be employed by uniformly dispersing.

As the photo-degradation accelerator, for example, there can beexemplified benzoins, benzoin alkyl ethers, benzophenone and derivativesthereof such as benzophenone, and 4,4′-bis(dimethylamino)benzophenone;acetophenone and derivatives thereof such as acetophenone andα,α-diethoxyacetophenone; quinones; thioxanthone; a photo-exciting agentsuch as phthalocyanine, an anatase-type titaniumoxide, anethylene-carbon monoxide copolymer, and an accelerator such as anaromatic ketone and a metal salt thereof, etc. The photo-degradationaccelerators can be employed solely or in combination of two or morekinds. By the use of the photo-degradation accelerators, a celluloseester can be photo-decomposed. For that reason, biodegradability can beinterdependently elevated upon the photo-degradability.

As the accelerators for biodegradation, there are exemplified, forexample, an organic acid such as an oxo acid (for example, an oxo acidhaving a carbon number of 2-6 or so such as glycolic acid, lactic acid,citric acid, tartaric acid, and malic acid), a saturated dicarboxylicacid (for example, a lower saturated dicarboxylic acid having a carbonnumber of 2-6 or so such as oxalic acid, malonic acid, succinic acid,succinic anhydride, and glutaric acid); a lower alkyl ester of theorganic acids with an alcohol having a carbon number of 1-4 or so. Apreferred accelerator for biodegradation includes citric acid, tartaricacid, and malic acid which are an organic acid having a carbon number of2-6 or so.

The accelerators for biodegradation are employed solely or incombination.

Further, as the accelerators for biodegradation, there are also includeda hydrolysis enzyme such as biodegradable enzyme, for example, lipase,cellulase, and esterase, etc. The biodegradable enzyme can be employedby suspending or dispersing in a solvent. It is to be noted that theabove-mentioned accelerators for photodegradation can be employedtogether with the accelerators for biodegradation. Further, cellulosepowder can be also mixed in order to prevent an aggregation of coatedparticles.

In the present invention, the coating material is dissolved or dispersedin a solvent, and it is sprayed on the surface of the particle-statefertilizers while maintaining at a high temperature, and a high speedheated air stream is simultaneously blown to instantly dry and coat,whereby, the particle-state fertilizer can be obtained.

As the solvents, there can be enumerated ketones such as acetone and2-butanone (MEK), ketones such as cyclohexanone, esters such as methylformate, methyl acetate, and ethyl acetate, and cyclic ethers such asTHF and dioxane which are low in price and have an appropriate boilingpoint (70-90° C.), and THF is more preferred from a viewpoint of anexcellent solubility to the coating material II-A and the coatingmaterial II-B.

Hereinafter, the No. III of the invention is illustrated.

In the beginning, the cyclic ester-modified cellulose ester isillustrated which is employed for the coating material III-A in thepresent invention.

The cyclic ester-modified cellulose ester in the present invention is aproduct in which a cyclic ester is graft-modified by a ring-openingpolymerization into a cellulose ester having hydroxyl groups.

The cellulose esters having hydroxyl groups is a product in which thehydroxyl groups in a cellulose are partially esterified by a fatty acidand inorganic acid, for example, there are exemplified a celluloseacetate, a cellulose acetate propionate, a cellulose butylate, and acellulose acetate phthalate, a cellulose nitrate, a mixed ester such asa cellulose nitrate-acetate. The cellulose esters may be employed solelyor in combination of one or more kinds. Of the cellulose esters, thereare preferred the esters of an organic acid such as the celluloseacetate, a cellulose acetate propionate, and cellulose acetate butylate.Particularly, the cellulose acetate is useful.

Hereinafter, an ester by a fatty acid (a fatty acid cellulose ester) isillustrated as a typical example.

Ester bond is 1-2.9 pieces on average, that is, a substitution degree ispreferably 1-2.9, which is composed of the fatty acid and hydroxylgroups in glucose units of the cellulose. Accordingly, residual hydroxylgroup is 0.1-2 pieces on average, particularly, more preferably 0.2-0.9piece on average.

In the case that the substitution degree is less than the range, when itis coated by the cyclic ester-modified cellulose ester, water resistancelowers in the surface of the particle-state fertilizer and, in the caseof exceeding the range, there remarkably lower not only a compatibilitywith other components and flowability in melting, but alsobiodegradability.

It is to be noted that the substitution degree DS in the celluloseester, as an example in the case of the cellulose acetate, when acombined acetate acid % (acetylated degree) is X, and Y is X/100, iscalculated by the equation described below.Substitution degree DS=(162×Y)/(60−42×Y)

The cyclic ester, which is employed for allowing to react with thecellulose ester, is not particularly limited, if it can be ring-openingpolymerized, and there are enumerated ones exemplified in the No. I ofthe present invention. Likewise, there are also enumerated glycolide andlactide which are exemplified in the No. I of the present invention. Thecyclic ester in the present invention is not limited to a unitary one,and there may be combined a plurality of the above-described variousones.

It is to be noted that as the cyclic ester, ε-caprolactone is preferredin view of readily obtaining and relatively low price, and which isexcellent in compatibility with the fatty acid cellulose ester such asthe cellulose acetate in the present invention.

There is not particularly limited a feeding ratio of the fatty acidcellulose ester having hydroxyl groups with respect to the cyclic esterwhich is employed for obtaining the cyclic ester-modified fatty acidcellulose ester, and the cyclic ester is desirably 99-15% by mass basedon 1-85% by mass of the fatty acid cellulose ester having hydroxylgroups (total of both is 100% by mass). In the case that the ratio ofthe fatty acid cellulose ester having hydroxyl groups exceeds 85% bymass, viscosity is remarkably elevated in a reaction system, resultingin becoming difficult in handling. Contrarily, in the case that it isless than 1% by mass, productivity lowers. In the case that ductility isrequired, it is preferred to elevate the feeding ratio of the cyclicester.

In the case that it is difficult to handle because of a too highviscosity, it is also possible to lower the viscosity in the reactionsystem for allowing to readily react by adding supplementary thirdcomponents which include an organic solvent not having an activehydrogen or a polyvalent alcohol having a reactivity, and which areexcellent in compatibility with the fatty acid cellulose ester and thecyclic ester.

As catalysts to be employed in a graft polymerization reaction of thecyclic ester, particularly, the lactones with the fatty acid celluloseester having hydroxyl groups, there are enumerated catalystsconventionally employed in a ring-opening reaction of the cyclic ester,for example, an alkali metal such as sodium and potassium or aderivative such as an alkoxide, an organic metal or a metal complex suchas an alkyl aluminum typified by triethyl aluminum and a derivativetherefrom, an alkoxy titanium typified by tetrabutyl titanate, tinoctylate and dibutyltin dilaurate, and inorganic tin such as a metalhalide, etc.

It is to be noted that tin octylate is a catalyst to be preferablyemployed for preparing the cyclic ester-modified fatty acid celluloseester in the present invention.

For obtaining the cyclic ester-modified fatty acid cellulose ester whichis a graft polymer in the present invention, there is preferablyemployed a twin-screw extruder in addition to a usual reactor equippedwith an agitator and a condenser (equipped with a drying tube) as areaction apparatus.

As a temperature in a polymerization for obtaining the graft polymer inthe present invention, there is preferred a temperature which is appliedfor a ring-opening polymerization of the cyclic ester, and it ispreferably 100-210° C.

Further, reaction time of period for the polymerization depends upon akind of the fatty acid cellulose ester having hydroxyl groups and thecyclic ester, feeding ratio thereof, a kind and amount of the catalyst,reaction temperature, and reaction apparatus, and although it is notparticularly limited, it is preferably 1-8 hours.

Still further, in the case of obtaining the graft polymer, respectiveraw materials, nitrogen, and the apparatus, etc. in the polymerizationreaction are desirably employed after sufficiently dried.

Besides, moisture content in the reaction system is not more than 0.1%by mass, preferably not more than 0.01% by mass, and more preferably notmore than 0.001% by mass.

Molecular weight in the graft copolymer thus-obtained, that is, thecyclic ester-modified fatty acid cellulose ester depends upon amolecular weight in the fatty acid cellulose ester having hydroxylgroups and a kind of the cyclic ester to be grafted, and a mass-averagemolecular weight is preferred in 200,000-2,000,000, and more preferredin 300,000-1,000,000. In the case that the mass-average molecular weightis less than 200,000 in the graft copolymer, for example, when a fattyacid cellulose ester, for example, a cellulose acetate having amass-average molecular weight of 157,000 is employed as a startingmaterial, the amount of the cyclic ester to be added is small, andductility is apt to become insufficient in the coating material III-Aobtained from the graft polymer. In the case of exceeding 2,000,000,viscosity becomes too high in the graft polymer, resulting in that aproblem in a coating thin layer is apt to be caused.

In the average graft polymer obtained by the polymerization reaction insuch the feeding ratio of the fatty acid cellulose ester having hydroxylgroups with the cyclic ester, the cyclic ester, for example,ε-caprolactone is preferably 2-50 mol, more preferably 3-30 mol withrespect to residual hydroxyl groups in the glucose unit, and there ismost preferred the cyclic ester having a structure by additionpolymerization of 5-20 mol.

By an internal plasticizing effect in the fatty acid cellulose ester byaddition of the cyclic ester, a melting temperature in a product can belowered and thermal decomposition temperature can be elevated. By theeffect, coating can be conducted without adding a large amount of aplasticizer by an apparatus to be employed for coating of usualthermoplastic resins.

Further, since a coating thin layer internally-plasticized by the cyclicester in the present invention does not show a migrating property, eventhough a molded article is placed in a contact state with other moldedarticles under a high temperature and moisture, it is not anxious thatit damages the other molded articles.

The cyclic ester-modified fatty acid cellulose ester to be employed inthe present invention may be employed solely or, so far as containing acyclic ester-modified fatty acid cellulose ester, it may be evenconstructed by a composition (it is prepared from a mixture composed ofa plurality of fatty acid cellulose esters having a differentsubstitution degree) containing a variety of the cyclic ester-modifiedfatty acid cellulose esters having a different substitution degree. Suchthe composition may contain other cellulose esters such as celluloseesters having a high substitution degree in the case of employing as thecoating material III-B which is described hereinafter.

Substitution degree in the cellulose esters having a high substitutiondegree contains a cellulose esters having a high substitution degree(for example, substitution degree of not less than 2.2, preferably notless than 2.4) which is poor in biodegradability.

Further, a preferred cellulose esters having a high substitution degreefrequently has an identical or similar substitution group to thepreviously-described fatty acid cellulose ester having hydroxyl groupsand, particularly, it frequently has an identical substitution group. Inthe case that the fatty acid cellulose ester is a cellulose acetate, theidentical or similar substitution group includes an ester residual groupof an organic acid having a carbon number of 1-4 or so.

The composition containing a plurality of the cyclic ester-modifiedfatty acid cellulose esters having a different substitution degree ischaracterized in that even though there is low a content of the cyclicester-modified fatty acid cellulose esters, biodegradability can beelevated in the coating thin layer.

The content of the cyclic ester-modified fatty acid cellulose esters isnot less than 10% by mass, preferably not less than 10-90% by mass, andmore preferably not less than 10-75% by mass or so (for example, 10-50%by mass) based on total amount of the fatty acid cellulose esters andthe cyclic ester-modified esters (a graft polymer). In the case that thecontent of the cyclic ester-modified fatty acid cellulose esters is notless than 10% by mass, biodegradability can be jumpingly elevated in acellulose ester having a poor biodegradability. It is to be noted thatwhen the content of the graft polymer increases in the cellulose estershaving a low substitution degree, a cellulose ester composition can bedecomposed by biodegradation within a short time of period.

A mechanism of biodegradation is not distinct in such the composition.However, it is guessed that there are cultivated microorganisms which donot inherently have degradability for the cellulose esters having a highsubstitution degree by allowing to contain a small amount of thecellulose esters having a low substitution degree, resulting in that thecellulose esters having a high substitution degree can be alsodecomposed.

It is to be noted that the cellulose esters which are a starting rawmaterial can be prepared by a common method regardless of high or lowsubstitution degree.

Further, the substitution degree of the cellulose esters may be adjustedby a one-stage reaction in a reaction of an organic acid or an acidanhydride with a cellulose and, the substitution degree may be adjustedby hydrolysis after the preparation of the cellulose esters having ahigh substitution degree (for example, 3-substituted esters).

Substances to be employed as the coating material III-B in the presentinvention are the substances exemplified in the No. II of the presentinvention.

Still further, as the coating material in the present invention, therecan be optionally employed third components for a coating thin layerwhich can be mixed. In the present invention, there can be furtheroptionally employed fourth components for a coating thin layer. Thethird components (it is represented by coating material III-C in TableIII-1 of Example) and fourth components for a coating thin layer are asdescribed in the No. II of the present invention, and those can belikewise employed as in the second aspect of the present invention.

In the present invention, the coating material is dissolved or dispersedin a solvent, and it is sprayed on the surface of the particle-statefertilizers while maintaining at a high temperature, and a high speedheated air stream is simultaneously blown to instantly dry and coat,whereby, the particle-state fertilizer can be obtained.

As the solvents, since the cellulose acetate having a low substitutiondegree shown in the above-described JP-A-11116371 Official Gazette ispoor in solubility into solvent, although there are employedcyclohexanone, methyl formate, methyl acetate, THF, dioxane, andacetone, of those, there are not solvents having an appropriate aboiling point (70-90° C.) at which an operability is good. For example,THF has a boiling point of 65° C. which is a little low, and it isexpensive.

On the other hand, the cyclic ester-modified fatty acid cellulose estersuch as a lactone-modified cellulose ester can be dissolved in ethylacetate and 2-butanone (MEK) in addition to the above-describedsolvents. Ethyl acetate and 2-butanone have a boiling point ofapproximately 80° C., and lower in price compared to THF.

Hereinafter, the No. IV of the invention is illustrated.

The fatty acid cellulose esters having hydroxyl groups in the presentinvention is a product in which the hydroxyl groups in a cellulose arepartially esterified by a fatty acid and inorganic acid, for example,there are exemplified cellulose esters such as a cellulose acetate, acellulose acetate propionate, a cellulose acetate butylate, and acellulose acetate phthalate, and a cellulose nitrate. Of the celluloseesters, there are preferred the cellulose acetate, a cellulose acetatepropionate, and cellulose acetate butylate, and particularly, thecellulose acetate is useful.

Ester bond is 1-2.9 pieces on average, that is, a substitution degree ispreferably 1-2.9, which is composed of the fatty acid and hydroxylgroups in glucose units of the cellulose. Accordingly, residual hydroxylgroup is 0.1-2 pieces on average, particularly, more preferably 0.2-0.9piece on average.

The cyclic ester in the present invention is as described in the No. IIIof the invention.

There is not particularly limited a feeding ratio of the fatty acidcellulose ester having hydroxyl groups with respect to the cyclic esterwhich are employed for obtaining the fatty acid cellulose esterderivative in the present invention, and it can be appropriatelyselected depending upon a mode for employing as a base fill for amarking film. For example, in the case that the marking film is stuck ona curved surface, since ductility is required in the base fill for amarking film, the feeding ratio of the cyclic ester is preferablyelevated. Polymerization for allowing to graft the cyclic ester to thefatty acid cellulose ester having hydroxyl groups is as described in theNo. III of the invention.

Molecular weight in a reaction product obtained as described hereinabovedepends upon a molecular weight in the fatty acid cellulose ester havinghydroxyl groups which is a raw material and a kind of the cyclic esterto be grafted. A mass-average molecular weight is preferred in a rangeof 200,000-2,000,000, and more preferred in 300,000-1,000,000. In thecase that the mass-average molecular weight is less than 200,000 in thegraft copolymer, when a cellulose acetate has a mass-average molecularweight of 157,000, the amount of the cyclic ester to be added is small,and ductility is apt to become insufficient in the base film for amarking film obtained from the graft polymer. In the case of exceeding2,000,000, viscosity becomes too high in the graft polymer, resulting inthat a problem in molding is apt to be caused.

In the average graft polymer obtained by the polymerization reaction insuch the feeding ratio of the fatty acid cellulose ester having hydroxylgroups with the cyclic ester, the cyclic ester, for example,ε-caprolactone is preferably 2-50 mol, more preferably 3-30 mol withrespect to residual hydroxyl groups in the glucose unit, and there ismost preferred the cyclic ester having a structure by additionpolymerization of 5-20 mol.

By an internal plasticizing effect in the fatty acid cellulose ester byaddition of the cyclic ester, a melting temperature in a product can belowered and thermal decomposition temperature is elevated. By theeffect, a mold-fabricating can be conducted without adding a largeamount of a plasticizer by usual means for molding thermoplastic resins,for example, injection molding and compression molding.

Further, since a coating thin layer internally-plasticized by the cyclicester in the present invention doe not show a migrating property, eventhough a molded article is placed in a contact state with other moldedarticles under a high temperature and moisture, it is not anxious thatit damages the other molded articles.

Still further, the fatty acid cellulose ester derivative in the presentinvention may be employed together with one or a mixture of a variety ofstabilizers such as an anti-oxidant and an ultraviolet ray absorbent,and additives such as dyes and pigments, fillers, lubricants, staticagents, and flame retardants according to purposes thereof as well as ausual resin or resin composition.

As a method for molding the fatty acid cellulose ester derivative forthe use as a base film for a marking film, there are preferably utilizeda casting molding method and calendar molding method, and the castingmolding method is particularly preferred.

In the preparation of a film by the casting molding method, anappropriate plasticizer or solvent is added and mixed to the fatty acidcellulose ester derivative to once prepare a fatty acid cellulose esterderivative composition. In the case, other additives as describedhereinabove can be also optionally added and mixed.

Since thus-obtained fatty acid cellulose ester derivative compositioncan provide a desired shape by freely flowing by the gravitational forcealone without necessity of giving a special external force, it canprovide a desired casting film through the film-preparation by thermallydrying alone a solution. As heating and drying conditions in the case,for example, there can be exemplified conditions such as approximately30-200° C. and approximately 2-120 minutes.

Hereinafter, the No. V of the invention is illustrated.

A cyclic ester-modified cellulose derivative to be employed in thepresent invention is obtained by grafting of a cyclic ester into acellulose ester having hydroxyl groups. The cellulose ester havinghydroxyl groups which is employed as a raw material is a product inwhich the hydroxyl groups in a cellulose are partially esterified oretherized by a fatty acid and inorganic acid. As the cellulose esterhaving hydroxyl groups, for example, there are enumerated celluloseesters such as a cellulose acetate, a cellulose acetate butylate, acellulose acetate propionate, a cellulose acetate phthalate, and acellulose nitrate, or cellulose ethers such as an ethyl cellulose, amethyl cellulose, a hydroxyethyl cellulose, and a hydroxypropylcellulose, etc. Of those, cellulose fatty acid esters are preferablyemployed in the present invention because of a relatively low price andreadily obtaining in an industrial fashion and, further, the celluloseacetate, the cellulose acetate butylate, and the cellulose acetatepropionate are preferred because of readily handling.

Ester bond is 1-2.9 pieces on an average, that is, a substitution degreeis preferably 1-2.9, which is composed of the fatty acid and hydroxylgroups in glucose units of the cellulose.

Accordingly, residual hydroxyl group is 0.1-2 pieces on average,particularly, more preferably 0.2-0.9 piece on average.

Particularly, there are preferred a cellulose acetate having asubstitution degree of acetyl groups of 1.5-2.8 (an acetylated degree of39-60%), a cellulose acetate propionate having a substitution degree ofpropionyl groups of 0.5-2.8 (a propionylated degree of 12-63%) and asubstitution degree of acetyl groups of 0.5-2.8 (an acetylated degree of16-60%), and a cellulose acetate butylate having a substitution degreeof butyryl groups of 0.5-2.5 (a butyrylated degree of 14-67%) and asubstitution degree of acetyl groups of 0.5-2.8 (an acetylated degree of16-60%).

The cyclic ester in the present invention, which is employed forallowing to cyclic ester-modify, that is, to graft polymerize with thecellulose derivative having hydroxyl groups, is as described in the No.III of the present invention.

In the present invention, there is not particularly limited a feedingratio of the cellulose derivative having hydroxyl groups with respect tothe cyclic ester and, in order to modify by the cyclic ester, thecellulose derivative having hydroxyl groups is employed in 1-85% bymass, and preferably 30-70% by mass, and the cyclic ester is employed in15-99% by mass, and preferably 30-70% by mass. In the case that theratio of the cellulose derivative having hydroxyl groups exceeds 85% bymass, viscosity is remarkably elevated in a reaction system, resultingin becoming difficult in handling. Contrarily, in the case that theratio of the cellulose derivative having hydroxyl groups is less than 1%by mass, productivity lowers. It is to be noted that in the case of aparticularly high viscosity, a reacting processing apparatus in which atwin-screw extruder is optionally employed may be applied together withan apparatus for recovering monomers by distilling out in vacuo.

Further, in the case of a high viscosity, there may be employed anorganic solvent not having an active hydrogen which is excellent incompatibility with cellulose acetate and the cyclic ester as a thirdcomponent, whereby, viscosity in the system can be lowered to a rangecapable of readily handling.

As the solvents, there can be enumerated ketone-based or ester-basedsolvents such as acetone, methylethyl ketone, methylisobutyl ketone,ethyl acetate, butyl acetate, and cellosolve acetate, or a mixed solventthereof.

As catalysts to be employed in a graft-polymerization reaction of thecyclic ester with the cellulose derivative having hydroxyl groups, thereare enumerated catalysts conventionally employed in a ring-openingreaction of the cyclic ester, for example, an alkali metal such assodium and potassium or a derivative such as an alkoxide, an organicmetal such as tin octylate and dibutyltin dilaurate, and a metal halidesuch as stannous chloride, etc., in usual, which are widely described inliteratures.

However, a preferred catalyst to be employed in the present invention istin octylate. Further, reaction time of period depends upon a kind ofthe cellulose derivative having hydroxyl groups and the cyclic ester,feeding ratio thereof, a kind and an amount of the catalyst, reactiontemperature, and reaction apparatus, and although it is not particularlylimited, it is preferably 1-8 hours. Particularly, in the case ofemploying the twin-screw extruder together with an apparatus forrecovering monomers by distilling out in vacuo, a purpose can be alsoattained by exceedingly shortening the reaction time of period to notmore than 10 minutes.

Still further, in the case of obtaining the graft polymer, respectiveraw materials, nitrogen for purging a reactor, and the reactor, etc. aredesirably employed after sufficiently dried.

Moisture content in the reaction system is not more than 0.1%,preferably not more than 0.001%. The reaction temperature is preferablya temperature at which a ring-opening polymerization of a cyclic esteris usually conducted, and it is preferably 100-210° C.

Molecular weight in thus-obtained cyclic ester-modified cellulosederivative depends upon a molecular weight in the cellulose derivativehaving hydroxyl groups and a kind of the cyclic ester to be grafted. Amass-average molecular weight (conventionally, it is referred to as aweight-average molecular weight) is preferred in a range of50,000-1,000,000.

Average graft polymer obtained by the polymerization reaction in suchthe feeding ratio of the cellulose derivative having hydroxyl groupswith the cyclic ester, the cyclic ester, for example, ε-caprolactone hasa structure containing 1-50 mol of ε-caprolactone, preferably 2-50 mol,more preferably 2-30 mol, and particularly preferably 2-20 mol based on1 mol of the glucose unit.

Heat-transfer picture image-recording material is obtained by coating asolution of the cyclic ester-modified cellulose derivative onto a basematerial to prepare a dye-receiving layer.

As the base material for the picture image-recording material, there canbe employed, for example, a paper made from natural materials, asynthetic paper (for example, a polypropylene-based, apolystyrene-based, and a polyester-based synthetic paper, etc.), aplastic film (for example, a polyester film such as a polyethyleneterephthalate film), or a laminate thereof, etc. A preferred base filmincludes the synthetic paper and the plastic film.

Thickness of the base material can be optionally selected from a rangeof, for example, 5-500 μm, preferably 10-300 μm, and more preferably50-200 μm or so. In the base material, particularly, the synthetic paperand the plastic film, there may be added stabilizers such as ananti-oxidant, an ultraviolet ray absorbent, and a thermal stabilizer,and additives such as lubricants, static agents, and pigments. Thepicture image-recording material has a dye-receiving layer containingthe above-described resins over at least one surface of the basematerial. The dye-receiving layer is formed by coating a coatingsolution containing the resins onto the base material, followed bydrying. The coating solution can be prepared using a resin compositionand an appropriate solvent.

As a method for coating the coating solution, there can be employed ausual method, for example, a roll-coating method such as a gravure andreverse method, a doctor-knife method, a knife-coating method, and anozzle-coating method, etc.

The dye-receiving layer in the picture image-recording material may beany one of a single layer and a laminated layer, usually, it is a singlelayer. Thickness of the dye-receiving layer can be optionally selectedfrom a range of, for example, not less than 0.1 μm (for example, 0.5-40μm), and preferably 1-30 μm or so according to the base material and usepurposes. The cyclic ester-modified cellulose derivative is employed in5-50% by mass, and preferably 10-40% by mass based on solid componentsof the dye-receiving layer.

The picture image recording material of the present invention isemployed in combination with a heat-transfer sheet containing asublimatable dye. The picture image-recording material of the presentinvention is useful for forming a picture image onto the pictureimage-recording material by a heat-transfer method, for example, inwhich a picture image-recording material is brought into contact with aheat-transfer sheet containing and a sublimatable dye and heated by athermal head to move a dye for heat-transferring onto the pictureimage-recording material.

Hereinafter, the No. VI of the invention is illustrated.

The cyclic ester-modified cellulose derivative to be employed in thepresent invention is illustrated as described in the No. V of theinvention.

As a substrate in the present invention, there can be employed a filmmade from a polycarbonate, a polyallylate, a polyetherimide, apolysulfone, a polyphenyl ether, a polyamideimide, a polyimide, apolyethylene naphthalate, a polyphenyl sulphide, a polyetheretherketone, and a fluorine resin, and a film made from a polyethyleneterephthalate, a polybutylene terephthalate, a polyethylene, apolypropylene, a polystyrene, a polyvinyl chloride, a polyvinylidenechloride, and a nylon, etc.

Preferably, it is a biaxially-oriented film.

As an ink layer having a heat-transferring property in the presentinvention, there is employed a melt type or sublimatable type ink layerhaving a heat-transferring property which is conventionallypublicly-known as it is, and it is not particularly limited. That is,the ink layer having a heat-transferring property to be employed in thepresent invention is constructed by coloring agents, waxes, and resins,and additives such as lubricants, surfactants, etc.

As the coloring agents, there are employed dyes and pigments such ascarbon black, an iron oxide red, a lakered C, a first skyblue, abenzidine yellow, copper phthalocyanine green, copper phthalocyanineblue, a direct dye, an oily dye, and a basic dye, etc. As the waxes,there are enumerated, for example, natural waxes such as a carnauba wax,an olicury wax, a canderrila wax, a japan wax, a cane wax, a montan wax,an ozokerite, a microcrystalline wax, an ceresine wax, and a paraffinwax, and synthesized waxes such as a Fischer-tropsh wax, a low molecularweight polyethylene, an oxidized wax, and a hydrogenated wax, etc.

Further, as the resins, there are exemplified, for example, avinyl-based resin such as a polyacrylic acid, a polyacrylate, apolymethacrylic acid, a polymethacrylate, a polyacrylic amide, apolystyrene, a polyvinyl acetate, a polyvinyl alcohol, a polyvinylbutylal alcohol, a polyvinyl pyrolidone, a polyvinyl chloride, apolyvinylidene chloride, a cellulose-based resin such as an ethylcellulose, a hydroxyethyl cellulose, an ethylhydroxy cellulose, ahydroxypropyl cellulose, a methyl cellulose, and a cellulose acetate, apolyester resin, a polyacetal resin, an epoxy resin, a terpene resin, arosin resin, a fluorine resin, and a silicone resin, etc.

As the additives, there can be employed a fatty acid, a metal salt of afatty acid, a fatty acid ester, a fatty acid amide, an inorganic salt, anonionic-based surface active agent, a cationic-based surface activeagent, an anionic-based surface active agent, and an ampholytic surfaceactive agent, etc., and those are not particularly limited.

The ink layer having a heat-transferring property can be formed by apublicly-known method. For example, a composition of the melt type inklayer having a heat-transferring property is specifically exemplified inExample VI-1, and a composition of the sublimatable type ink layerhaving a heat-transferring property is specifically exemplified inExample VI-3.

A heat-resistible protecting layer is formed by adjusting a viscosity ofthe cyclic ester-modified cellulose derivative using a solvent to modifyto a condition being capable of coating, by coating it onto an oppositesurface of the substrate on which the ink layer having aheat-transferring property is formed, and by drying at 50-150° C.

Proportion of the cyclic ester-modified cellulose derivative in theheat-resistible protecting layer is 40-100% by mass and, further,preferably 60-100% by mass based on solid components in theheat-resistible protecting layer. Thickness is 0.01-2.00 μm and,further, preferably 0.05-0.75 μm. As described hereinabove, there can beobtained a heat-transferring recording material in which the ink layerhaving a heat-transferring property is formed on the surface of thesubstrate, and the heat-resistible protecting layer composed of thecyclic ester-modified cellulose derivative is formed on the oppositesurface of the ink layer in the substrate.

Hereinafter, the No. VII of the invention is illustrated.

The conductive coating resin (A) to be employed in the present inventioncontains 2-20% by mass, preferably 5-15% by mass of a cellulose esterderivative (a) obtained by a ring-opening graft-polymerization of acyclic ester with a cellulose ester derivative having hydroxyl groupsand 98-80% by mass, preferably 95-85% by mass of a resin for coating (b)[total of (a) and (b) is 100% by mass].

In the case that an amount of the cellulose ester derivative (a) is lessthan 2% by mass, it becomes difficult to elevate conductivity in a driedcoating layer or undried coating layer, resulting in that an adheringefficiency of a finishing coating becomes worse. On the other hand, inthe case that an amount is more than 20% by mass, compatibility with theresin for coating (b) becomes worse, resulting in that a storagestability is unpreferably deteriorated in a coating composition.

The cellulose ester having hydroxyl groups in the present invention isas described in the illustration for the No. III of the presentinvention. Ester bond is 1-2.9 pieces on average, that is, asubstitution degree is preferably 1-2.9, which is composed of the fattyacid and hydroxyl groups in glucose units of the cellulose and,accordingly, residual hydroxyl group is 0.1-2 pieces on average,particularly, more preferably 0.2-1.3 piece on average.

The cyclic ester in the present invention is not limited, if it can bering-opening polymerized, and there are enumerated ones exemplified inthe No. III of the present invention.

There is not particularly limited a feeding ratio of the cellulose esterderivative having hydroxyl groups with respect to the cyclic ester whichis employed for obtaining the cellulose ester in the present inventionand, it can be appropriately selected according to a use mode of theconductive coating composition. In order to conduct the graftpolymerization of the cellulose ester having hydroxyl groups with thecyclic ester, the cyclic ester is desirably 99-15% by mass based on1-85% by mass of the fatty acid cellulose ester having hydroxyl groups.In the case that the ratio of the cellulose ester derivative havinghydroxyl groups exceeds 85% by mass, viscosity is remarkably elevated ina reaction system, resulting in becoming difficult in handling.

Contrarily, in the case that it is less than 1% by mass, acharacteristics such as a heat resistance is unpreferably lost in thecellulose ester.

In the case that it is difficult to handle because of too highviscosity, it is also possible to lower the viscosity in the reactionsystem for allowing to readily react by adding supplementary thirdcomponents which include an organic solvent not having an activehydrogen or a polyvalent alcohol having a reactivity, and which areexcellent in compatibility with the fatty acid cellulose ester and thecyclic ester.

Conditions for the preparation of the cellulose ester derivative (a)which is a graft polymer in the present invention are as described inthe No. III of the present invention.

A molecular weight of thus-obtained cellulose ester derivative (a)depends upon a molecular weight of the cellulose ester having hydroxylgroups and a kind of the cyclic ester to be grafted which are rawmaterials. Mass-average molecular weight (it is measured using ananalytical curve of a standard polystyrene in chloroform in GPC)preferably ranges in 50,000-1,000,000, and more preferably in80,000-800,000. In the case that the mass-average molecular weight isless than 50,000, strength of a coating layer is apt to becomeinsufficient in the conductive coating composition.

Further, in the case of exceeding 1,000,000, viscosity becomes too highin the graft polymer, and smoothness lowers in the coating layer,resulting in that a problem is apt to be caused in coating.

As the resin (b) for a coating to be employed in combination with thecellulose ester derivative, there can be employed conventionally-knownresins for a coating.

For example, there are enumerated a polyolefin-based resin such as achlorinated polypropylene resin, a maleic acid-modified chlorinatedpolypropylene resin, an ethylene-acrylic acid copolymer, and an EPDM (anethylene-diene terpolymer), a polybutadiene-based resin, a copolymerobtained by a graft-reaction of the polyolefin-based resin or thepolybutadiene-based resin with a radical polymerizable unsaturatedmonomer such as a (meth)acrylate or styrene, a thermoplastic resin suchas an epoxide-fatty acid ester-based resin, an alkyd-based resin, andacrylic-based resin, a thermosetting resin composed of a base resin suchas an acrylic-based resin, a polyester-based resin, an alkyd-basedresin, an epoxide-based resin, and urethane-based resin and acrosslinking agent (an amino resin and a blocked isocyanate compound),and an ordinary temperatures-curable resin composed of the base resinand the crosslinking agent (a polyisocyanate compound), etc.

The conductive pigment (B) to be employed in the present invention iscomposed of 40-60% by mass, preferably 45-5% by mass of a conductivecarbon black (c) and 60-40% by mass, preferably 55-45% by mass of ascaly graphite (d) [total of (c) and (d) is 100% by mass]. In the casethat formulating proportion of the conductive carbon black is less than40% by mass, and formulating proportion of the scaly graphite is morethan 60% by mass, there unpreferably lowers an adhering property in anarticle to be coated and a finishing coating layer. On the other hand,in the case that formulating proportion of the conductive carbon blackis more than 60% by mass, and formulating proportion of the scalygraphite is less than 40% by mass, physical properties unpreferablylower in the coating layer.

The conductive carbon black (c) to be employed in the present inventionis a powder-state substance primarily containing carbon, and itself isalready known. For example, it can be employed by appropriatelyselecting from a method for the preparation of a thermal black, afurnace black, a lamp black, a contact black (channel black, roll black,and disk black).

Further, as the conductive carbon black (c), there is preferablyemployed one having a DBP (dibutyl phthalate) absorbing amount rangingin 70-250 ml/100 g, preferably 100-200 ml/100 g and an electricalresistivity ranging in not more than 1 Ω·cm, preferably not more than0.1 Ω·cm. In the case that the DBP absorbing amount is less than 70ml/100 g, since a large amount of the conductive carbon black isrequired in order to elevate the conductivity of the coating layer, itis anxious that physical properties unpreferably lower in the coatinglayer. On the other hand, in the case that the DBP absorbing amount ismore than 250 ml/100 g, a storage stability occasionally tends tounpreferably lower in a coating composition, and a finishing outerappearance tends to unpreferably lower in a finishing coating. Further,in the case that the electrical resistivity is more than 1 Ω·cm, astorage stability occasionally tends to unpreferably lower in a coatingcomposition and physical properties unpreferably lower in the coatinglayer because of a large use amount.

As a preferred specific example of the conductive carbon black (c),there can be enumerated, for example, Vulcan XC-72 (manufactured byCabot. Corp.), CONDUCTEX 900, CONDUCTEX 975 (both are manufactured byColumbian Chemicals Company), and DENKA HS-100 (manufactured by DenkiKagaku Kogyo, Ltd.), etc.

It is to be noted that the DBP absorbing amount and the electricalresistance were measured by testing methods described below.

DBP absorbing amount: 1.00±0.01 g of a dried sample is preciselyweighed, and it is moved onto a plain glass plate or stone plate havingnot less than approximately 300×300 mm. If it is particle-state,particles are crushed with a spatula while appropriately compressing.Appropriately ½ of a necessary amount of DBP is slowly poured from aburette onto the plain glass plate or stone plate, and DBP is circularlyand uniformly spread, and then, a sample is gradually scattered bymoving onto DBP, followed by carefully kneading like drawing a smallcircle with the spatula.

The sample adhered to the spatula is removed by another spatula, andapproximately ⅓-¼ of DBP is further added, followed by repeating thesame operations to adjust a mixture to a uniform state. When nearing aterminating period, it is added one drop by one drop, and when furthernearing the terminating period, it is added ½ drop by ½ drop, andoperations are terminated at a period that a whole becomes a shrunklump. The operations are adjusted as terminating within 10-15 minutes,and the absorbing amount is calculated according to the followingequation by monitoring a DBP dropwise amount in the burette at 3 minutesafter a lapse of the operations.OA=(V/W)×100

-   -   wherein    -   OA: absorbing amount (ml/100 g)    -   V: use amount (ml) of DBP until a termination period    -   W: weight (g) of a dried sample

Electrical resistivity: Approximately 0.25 g of a dried sample is packedin an insulating cylindrical vessel, and sample amount is adjusted to asample height of 10±0.5 mm when the sample is compressed by pressure of50±1 kg/cm², and then, electrical resistivity (Ω·cm) is calculatedaccording to the following equation from electric potential difference,electric current, packing height of the sample, and cross-sectional areaunder the pressure.ρ=(S/L)×R

-   -   wherein    -   R=V/A    -   ρ: Electrical resistivity (Ω·cm)    -   S: Cross-sectional area of a sample (cm²)    -   L: Packing height (cm) of a sample    -   R: Electrical resistance (Ω)    -   V: Electric potential difference (V)    -   A: Electric current (A)

The scaly graphite (d) is powder-state, thickness ranges in not morethan 0.5 mm, and average particle diameter ranges in 0.5-15 μm, andpreferably 1-7 μm.

In the case that the thickness is more than 0.5 mm, the use amountbecomes large, there unpreferably tend to lower storage stability of acoating and physical properties of a coating layer.

In the case that the average particle diameter is less than 0.5 μm,conductivity of the coating layer is not sufficient and, on the otherhand, in the case that the average particle diameter is more than 15 μm,workability tends to lower in spray coating, and there unpreferably tendto lower adhesion, etc. to an article to be coated and a finishingcoating layer.

As a preferred specific example of the scaly graphite (d), there can beenumerated graphite powders SP-10, SP-20, HAG-15, HAG-150, and HAG-300(those are manufactured by Nihon Kokuen, Ltd.), and artificial graphitesPOG-2, POG-10, and POG-20 (those are manufactured by Sumitomo Chemicals,Ltd.), which are a trade name.

The above-described conductive resin for a coating (A) and conductivepigment (B) are formulated in a proportion of 75-85% by mass, preferably78-82% by mass of the conductive resin for a coating (A) and 25-15% bymass, preferably 22-18% by mass of the conductive pigment (B) (total ofthe (A) and the (B) is 100% by mass).

In the case that the formulating amount of the conductive resin for acoating (A) is less than 75% by mass and the formulating amount of theconductive pigment (B) exceeds 25% by mass, there unpreferably lowerphysical properties of the coating layer and there unpreferably lowersan adhesion to an article to be coated and a finishing coating layer. Onthe other hand, in the case that the formulating amount of theconductive resin for a coating (A) exceeds 85% by mass and theformulating amount of the conductive pigment (B) is less than 15% bymass, there cannot be unpreferably formed a coating layer which isexcellent in conductivity.

The coating composition of the present invention is preferably employedas a solvent-type coating in which an organic solvent is a medium, and anon-aqueous dispersion coating.

As the organic solvent, if it dissolves or disperses the above-describedresins, it can be limitedly employed and, specifically, there can beenumerated an aromatic hydrocarbon such as benzene, toluene, and xylene,an aliphatic hydrocarbon such as hexane, heptane, octane, and decane, achlorinated hydrocarbon such as trichloroethylene, perchloroethylene,dichloroethylene, dichloroethane, and dichlorobenzene, a ketone-basedsolvent such as methylethyl ketone and diacetone alcohol, analcohol-based solvent such as ethanol, propanol, and butanol, and acellosolve-based solvent such as methylcellosolve, butylcellosolve, andcellosolve acetate, etc.

In the coating composition of the present invention, there can beformulated other pigments in addition to the above-described conductivepigments. As the other pigments, if those are employed for usualcoatings, those are not particularly limited, and those are roughlydivided into an inorganic pigment and an organic pigment which aredescribed below.

As the inorganic pigments, there are enumerated white color-based oneswhich include titanium oxide, zinc oxide, basic lead carbonate, basiclead sulphate, a phosphate such as zinc phosphate, a molybdate such ascalcium molybdate, black color-based ones which include carbon black,rosin black, graphite, and iron black, yellow color-based ones whichinclude yellow lead, synthesized iron oxide yellow, transparent ironoxide, titanium yellow, zinc yellow, and strontium chromate, redcolor-based ones which include iron oxide, transparent iron oxide, redlead, molybdate orange, cuprous oxide, basic lead chromate, and leadcyanamide, green color-based ones which include chromium oxide andchromium green, blue color-based ones which include iron blue,ultramarine blue, and cobalt blue, extender pigments which includecalcium carbonate, barium sulphate, talc, clay, mica, silica, andplaster, non-conductive metal powder which includes a surface-oxidizedaluminum powder and lead suboxide powder, and pearly pigment, etc.

Further, as the organic pigments, there are enumerated an azolake-basedone which includes a β-naphthol-based one, a β-oxynaphthoic acid-basedone, a naphthol AS-based one, an acetoacetic anilide, an insolubleazo-based one which includes a β-naphthol-based one, naphthol AS-basedone, an acetoacetic anilide-based one, and a pyrazolone-based one, acondensed azo-based one which includes a naphthol AS-based one and anacetoacetic anilide-based one, a polycyclic pigment which includesanthraquinone-based one, phthalocyanine-based one, quinacridone,isoindorinone, dioxadine, perylene, perynone, thioindigo, pyrocholine,fluorubine, and quinophthalone, and metal complex-based ones, etc.

Further, in the coating composition of the present invention, there canbe optionally added a variety of additives such as a plasticizer, adispersant, a modifier for a coating surface layer, a fluiditycontroller, an ultraviolet ray absorbent, an ultraviolet ray stabilizer,an anti-oxidant, an accelerator for a crosslinking reaction, adepressant for a crosslinking reaction, which are publicly-known. Inorder to prepare the coating composition of the present invention usingthe above-described substances, there may be employed same apparatusesand processes as in conventional methods for the preparation ofcoatings. For example, a coating can be prepared by a method in whichpigments are dispersed in a mixture of a binder with a solvent using anappropriate dispersing apparatus such as a ball mill, a sand mill, and aroll mill to prepare a pigment paste, and necessary components arefurther added and uniformly mixed by a Disper. The coating compositionof the present invention can be applied to a nonconductive or conductivematerial or a material in which it is desired to further elevate aconductivity and, as the materials, there are enumerated plasticmaterials, reinforced plastic materials, and inorganic materials, etc.

The coating composition of the present invention can be coated byconventional coating methods. That is, coating can be conducted by meanssuch as an air spray coating, an airless spray coating, a variety ofstatic coating, a roll coating, and a brush coating.

Thickness of a coating layer usually ranges in approximately 5-40 μm,and preferably 10-25 μm based on thickness of a dried coating layer.Further, the coating layer is dried at room temperature or forciblyuntil surface resistance to be desired attains to 1×10⁶ Ω/cm in thecoating layer.

The coating layer formed by the coating composition of the presentinvention can be utilized as a coating layer for shieldingelectromagnetic wave or, an intermediate-coating or a staticunder-coating layer for finishing coating.

As the intermediate-coating, there can be employed an already knownintermediate-coating itself which is excellent in adhesion, smoothness,clearness, and weatherability. Specifically, there can be enumerated athermosetting intermediate-coating which primarily contains a short oilhaving an oil length of not more than 30% or a long-short oil alkydresin, or oil-free polyester resin and an amino resin which are avehicle.

The alkyd resin and the polyester resin have a hydroxyl value of 60-140mg KOH/g and an acid value of 5-200 mg KOH/g, in which an unsaturatedoil (an unsaturated fatty acid) is preferably employed as an oil to bemodified. Further, as the amino resin, there are appropriate analkyl(preferably, a carbon number of 1-5)-etherized melamine resin, aurea resin, and a benzoguanamine resin, etc.

As formulating ratio of the both resins, preferably, the alkyd resin and(or) the oil-free polyester resin are 65-85% by mass, and particularly70-80% by mass, and the amino resin is 35-15% by mass, and particularly30-20% by mass. Further, the amino resin can be partially changed to apolyisocyanate compound or a blocked polyisocyanate compound.

Further, as types of the intermediate-coating, there can be employed anorganic solvent-type one using the vehicles, a nonaqueous-dispersed typeone, a high solid type one, an aqueous solution type one, awater-dispersed-type one, and a powder type one, etc. which areconventionally publicly-known. Still further, there can be optionallyformulated extender pigments, coloring pigments, and other additives forcoatings in the intermediate coating.

The intermediate coatings are a coating for coating onto the surface ofthe conductive surface to be coated in the present invention, andcoating operation can be conducted by the same method as for theabove-described conductive coating. The thickness of the coating layerpreferably ranges in 10-50 μm based on a coating layer after curing.Temperature for curing the coating layer depends upon components in thevehicle, and in the case of heating, it ranges in 60-160° C. and,particularly, in 80-150° C.

The finishing coating is a coating for coating on the surface of theconductive coating layer or the surface of the intermediate coatings,and it gives a decorating property to an article to be coated.

Specifically, there can be employed an already known coating itselfbeing capable of forming a coating layer which is excellent in afinishing outer appearance (clearness, smoothness, and gloss),weatherability (a retention property of gloss, a keeping property ofcolor, and whitening-resistible property), chemical resistance, water ofcolor, and whitening resistible property), chemical resistance, waterresistance, moisture resistance, and curability, etc. For example, thereare enumerated a coating primarily containing an amino acrylic-basedresin, an amino alkyd-based resin, and an amino polyester-based resin asa vehicle and, further, there can be also applied a coating in which theamino resin is partially or wholly changed to a polyisocyanate compoundor a blocked polyisocyanate compound.

Type of the finishing coating is not particularly limited, and there canbe employed an organic solvent type one, a nonaqueous solvent-dispersedtype one, a water soluble (dispersed) type one, a powder type one, and ahigh solid type one, etc. Drying or curing of the coating layer isconducted by drying at ordinary temperature, drying at heating, andirradiation by active energy rays, etc.

The finishing coating to be employed in the present invention may beeven an any type of an enamel coating in which metallic pigments and(or) coloring pigments are formulated in the coating primarilycontaining the above vehicles, or a clear coating which does not containthe pigments at all or almost does not contain.

And, as a method for forming the finishing coating layer using thecoatings, for example, there are enumerated the following methods.

(1) a method (metallic- or solid-color finishing by a one-coat andone-baking style) in which there is coated and thermally cured ametallic coating composed of a metallic coating and optionally coloringpigments or a solid color coating containing coloring pigments.

(2) a method (metallic- or solid-color finishing by a two-coat andtwo-baking style) in which a metallic coating or a solid color coatingis coated, and then, thermally cured, followed by further coating aclear coating and thermally curing again by heating.

(3) a method (metallic- or solid-color finishing by a two-coat andone-baking style) in which a metallic coating or a solid color coatingis coated, and then, a clear coating is coated, followed bysimultaneously curing both coating layers by heating.

The finishing coatings are preferably coated by spray coating and anelectrostatic coating.

Further, thickness of the coating layer in the (1) ranges in 25-40 μmbased on a dried coating layer and, in the (2) and (3), in the case of ametallic coating or solid color coating, it preferably ranges in 10-30μm, and it preferably ranges in 25-50 μm in the case of a clear coating,respectively. Heating and curing condition can be freely selected bymaterials of an article to be coated and vehicle components, and it isusually 60-160° C., and particularly, preferably 100-150° C. for 10-40minutes.

In the present invention, by formulating the conductive carbon black (c)and the scaly graphite (d) at a specified proportion, since theconductive carbon black (c) forms a structure having a continuous chainstructure or a chain structure, and it exists in a coating compositionin the form in which the scaly graphite (d) aggregates with thestructure, it is not anxious that the conductive pigment (B) isseparated from the conductive resin for a coating (A) or sinks,resulting in that there is shown an effect of an excellent storagestability for a long time of period.

And, since the conductive carbon black and the scaly graphite in thecoating layer which are formed from those have a same structure as inthe above-descriptions, and these connect to each other, there can beeffectively reproduced an effect for elevating conductivity in thecoating layer.

Although functions in the cellulose ester derivative (a) are not clear,which is obtained by a ring-opening graft-polymerization of cyclicesters onto a cellulose ester having hydroxyl groups, it is presumedthat an effect is elevated by an action which allows to orientate sothat a scaly plain surface is opposite to surface to be coated. By theeffect, scales often come into contact with each other, and there can beshown an effect that conductivity in a coating layer is elevated by aconnection of the conductive carbon black (c) with the scaly graphite(d).

Hereinafter, the No. VIII of the present invention is illustrated indetail.

In the beginning, there are roughly shown symbols representingrespective components in the present invention and a relationshiptherebetween.

Cellulose ester derivative (a): It is obtained by a ring-opening graftpolymerization of cyclic esters with a cellulose ester having hydroxylgroups.

Polymerizable unsaturated monomer (b): It includes an unsaturatedmonomer having an isocyanate group (f), a polymerizable monomer (h), andother polymerizable monomers (g), etc.

Graft copolymer (I): It is obtained by a copolymerization of thecellulose ester derivative (a) with the polymerizable unsaturatedmonomer (b).

Unsaturated monomer having an isocyanate group (f)

Polymerizable monomer having an active hydrogen (h)

Polyisocyanate compound (c)

Polyisocyanate compound (II): It includes a polymer (e), etc. containingan isocyanate compound having a low molecular weight (d) and theunsaturated monomer having an isocyanate group (f) as constructingunits.

Isocyanate compound having a low molecular weight (d)

Polymer (e) containing the unsaturated monomer having an isocyanategroup

Oxazoline compound (II′)

Cellulose ester derivative (III): If it is the same kind as in thecellulose ester derivative (a), it may be not an identical one.

Modified vinyl-based copolymer (III′): It is obtained by acopolymerization of the cellulose ester derivative (III) (If it is thesame kind as in the above-described cellulose ester derivative (III)),it may be not an identical one) with other polymerizable unsaturatedmonomers (g).

Graft copolymer (IV): It is obtained by a copolymerization of a macromonomer (m) with other polymerizable unsaturated monomers (i) except it.

Other polymerizable unsaturated monomers (j) except it: It is component(b) other than component (h).

Nonaqueous-dispersed resin (V): It is a resin component in a dispersedliquid of a polymer (q) particle obtained by a polymerization of otherpolymerizable unsaturated monomers (g) in a nonaqueous solvent using asa dispersion stabilizer which is a polymer (p).

Polymer (p): a dispersion stabilizer, mass-average molecular weight of3,000-150,000.

Polymer (q): It is obtained by a polymerization of the polymerizableunsaturated monomer (g) in a nonaqueous solvent under the presence ofthe dispersion stabilizer (p), which has a glass transition temperatureof 0-100° C.

1. Cellulose Ester Derivative (a)

The cellulose ester derivative (a) to be employed in the presentinvention is obtained by a ring-opening graft polymerization of cyclicesters with a cellulose ester having hydroxyl groups. The celluloseester having hydroxyl groups is a product in which the hydroxyl groupsin a cellulose are partially esterified by an acid, and it is the sameas the cellulose ester derivative (a) in the VII of the presentinvention.

The cellulose ester derivative (a) obtained by a graft polymerizationincludes 2-50 mol, preferably 3-30 mol, and more preferably 5-20 mol ofε-caprolactone based on (0.1-2 pieces on average) of residual hydroxylgroups in glucose units as an average structure.

2. Polymerizable Unsaturated Monomer (b)

As the polymerizable unsaturated monomer (b) to be employed in thepresent invention, there are enumerated an unsaturated monomer having anisocyanate group (f), a polymerizable monomer having an active hydrogen(h), and other polymerizable unsaturated monomers (g).

As the other polymerizable unsaturated monomers (g), the followingsubstances are exemplified.

There are enumerated a (meth)acrylate which includes, for example, analkyl or cycloalkyl ester of (meth)acrylic acid having a carbon numberof 1-20 such as methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,octyl(meth)acrylate, lauryl(meth)acrylate, cyclohexyl(meth)acrylate,isobonyl(meth)acrylate, adamantyl(meth)acrylate, and an alkoxyalkylester of (meth)acrylic acid having a carbon number of 2-8 such asethoxybutyl(meth)acrylate, etc.

As substances other than the (meth)acrylate, there are enumerated, forexample, glycidyl(meth)acrylate, styrene, α-methylstyrene, vinyltoluene,(meth)acrylonitrile, (meth)acrolein, butadiene, and isoprene, etc.,these can be employed in combination.

As the polymerizable monomer having an active hydrogen (h), there areenumerated a (meth)acrylate containing a hydroxyl group and a(meth)acrylate containing an amino group which are described below, andwhich can be employed in combination.

As the (meth)acrylate containing a hydroxyl group, there are enumerated,for example, a hydroxyalkylester of (meth)acrylate having a carbonnumber of 2-8 such as hydroxyethyl(meth)acrylate andhydroxypropyl(meth)acrylate, Placcel FA-1 (a monomer in which 1 mol ofε-caprolactone is introduced into 1 mol of hydroxyethylacrylate),Placcels FM-1, FM-3, and FM-5 (a monomer in which 1 mol, 3 mol, and 5mol of ε-caprolactone is introduced into 1 mol of2-hydroxyethylacrylate, respectively) which is a commercially product byDaicel Chemical Industries, Ltd., which are a commercially product byDaicel Chemical Industries, Ltd., TONE-100 (a monomer in which 1 mol ofε-caprolactone is introduced into 1 mol of 2-hydroxyethylacrylate) whichis a commercially product by Union Carbide, Ltd. in USA, which are anadduct of 1-5 mol of lactones into 1 mol of the (meth)acrylatecontaining a hydroxyl group, and which can be employed in combination.

As the (meth)acrylate containing an amino group, there are enumerated,for example, an aminoalkyl ester of (meth)acrylic acid such asdimethylaminoethyl(meth)acrylate, diethylamino ethyl (meth)acrylate, and(meth)acryl amide, etc., and which can be employed in combination.

As the monomer having an isocyanate group (f), there are enumerated, forexample, isocyanate ethyl(meth)acrylate, isocyanatepropyl(meth)acrylate, isocyanate butyl(meth)acrylate, isocyanatehexyl(meth)acrylate, m-isopropenyl-α,α′-dimethylbenzyl isocyanate, andm-ethylenyl-α,α′-dimethylbenzyl isocyanate, etc. and, further, there isenumerated an unsaturated compound in which a polyisocyanate compoundsuch as hexamethylene diisocyanate is added to the polymerizable monomercontaining an active hydrogen (h) such as hydroxyethyl(meth)acrylate,and which can be employed in combination.

The polymerizable unsaturated monomer (b) exemplified as theabove-described (f), (g), and (h) can be employed also in combination,it is employed by selecting depending upon desired physical properties.

3. Graft Copolymer (I)

The graft copolymer (I) of the present invention is prepared by aradical polymerization of the above-described cellulose ester derivative(a) and unsaturated monomer (b) through a solution polymerization underthe presence of a radical polymerization initiator, the component (b)forms a trunk polymer (a trunk portion), and the component (a) forms abranched polymer, whereby, the graft copolymer (I) of the presentinvention can be obtained.

In the case that the polymerizable monomer having an active hydrogen (h)is employed as a portion of the polymerizable unsaturated monomer (b),and the polyisocyanate compound (c) is allowed to react with thepolymerizable monomer having an active hydrogen (h), it is prepared by aradical polymerization of the above-described cellulose ester derivative(a) with unsaturated monomer (b) through a solution polymerization underthe presence of a radical polymerization initiator, whereby, thecomponent (b) forms a trunk polymer, and the component (a) forms abranched polymer, and then, the polyisocyanate compound (c) is allowedto react with an active hydrogen in the monomer (h).

As the radical polymerization initiator, there can be employed aperoxide initiator such as benzoyl peroxide, t-butylhydroperoxide,cumylhydroperoxide, cumenhydroperoxide, t-butylperoxybenzoate, and anazo-based initiator such as t-butylperoxy-2-ethylhexanoate,azobisisobutyronitrile and azobisdimethyl valeronitrile,

As a solvent to be employed in the solution polymerization, there areenumerated benzene, toluene, xylene, an ester-based solvent such asbutyl acetate, ethyl acetate, propyl acetate, and cellosolve acetate, anether-based solvent such as dioxane and ethylene glycol dibutylether,and a ketone-based solvent such as methylethyl ketone and methylisobutyl ketone, etc., and which there can be employed solely or incombination of two or more kinds.

As use proportion of the components (a) and (b), the component (a) is1-30% by mass, and preferably 5-20% by mass, and the component (b) is70-99% by mass, and preferably 80-95% by mass (total of the (a) and (b)is 100% by mass).

In the case that the polymerizable monomer having an active hydrogen (h)is employed as a portion of the polymerizable unsaturated monomer (b),and the polyisocyanate compound (c) is allowed to react with thepolymerizable monomer having an active hydrogen (h), total of the (b)and (c) corresponds to 70-99% by mass of the (b).

In the case that the component (a) is less than 1% by mass, dryabilityand hardness become unpreferably insufficient in a coating layerobtained and, in the case that the component (a) exceeds 30% by mass,durability unpreferably lowers in a coating layer obtained.

The graft copolymer (I) of the present invention has an isocyanate groupat a trunk portion formed by the radical polymerization of thepolymerizable unsaturated monomer (b), and the content of the isocyanategroup is 0.5-28.5% by mass, and preferably 35-15% by mass based on thetotal mass of the graft copolymer (I). In the case that the content ofthe isocyanate group is less than 0.5% by mass, solvent resistance anddurability become poor in a coating layer obtained, unpreferablyresulting in that dryability and hardness also become insufficient and,on the other hand, in the case of exceeding 28.5% by mass, a coatinglayer becomes brittle, unpreferably resulting in that durability ratherlowers.

The graft copolymer (I) of the present invention is a polymer having anisocyanate group at a trunk portion and, in order to introduce anisocyanate group into the trunk portion, there can be applied methods(i) and (ii) described below.

-   -   (i): The above-described monomer having an isocyanate group is        employed as the polymerizable unsaturated monomer (b), or    -   (ii): Active hydrogen is introduced into a trunk portion of a        polymer which should become the copolymer (I) of the present        invention using the above-described polymerizable monomer having        an active hydrogen such as hydroxyl group or amino group as the        polymerizable unsaturated monomer (b), and more than equivalent        mol of the polyisocyanate compound is allowed to react with the        active hydrogen.

In the case that the polymerizable monomer having an active hydrogen (h)is employed as the polymerizable unsaturated monomer (b), as thepolyisocyanate compound which is allowed to react with theactive-hydrogen, there are enumerated aliphatic diisocyanates such ashexamethylene diisocyanate and trimethylhexamethylene diisocyanate,aliphatic group-substituted aromatic isocyanates such as xylylenediisocyanate, and cycloaliphatic diisocyanates such as isophoronediisocyanate, etc.

It is to be noted that in the case of employing the polyisocyanatecompound (c), total of the polymerizable monomers including the (c)corresponds to 70-99% by mass of the polymerizable monomer (b).

Thus-obtained graft copolymer (I) of the present invention has astructure that the component (b) forms a trunk polymer (a trunkportion), the trunk portion has an isocyanate group, and the component(a) forms a branched polymer.

Mass average molecular weight (it is measured using a curve of astandard Polystyrene in chloroform by a GPC) of the graft copolymer (I)is 2,000-150,000, preferably 5,000-50,000, and glass transitiontemperature is 0-90° C., preferably 15-75° C. In the case that the massaverage molecular weight is less than 2,000, it is unpreferablydifficult to obtain a satisfied dryability and hardness in a coatinglayer obtained and, on the other hand, in the case of exceeding 150,000,storage stability lowers, and it is unpreferably difficult to obtain afinishing property in a coating layer obtained. Further, in the casethat the glass transition temperature is less than 0° C., it isunpreferably difficult to obtain a satisfied dryability and hardness ina coating layer obtained and, on the other hand, in the case ofexceeding 90° C., coating layer becomes brittle, resulting in thatdurability rather unpreferably tends to lower.

The graft copolymer (I) of the present invention can provide a coatingthin layer by moisture curing alone.

4. Coating Composition

The present invention provides a single-liquid type coating compositionprimarily containing the graft copolymer (I), and optionally contains avariety of curing agents and resinous components.

That is, the coating composition of the present invention is comprisedthe graft copolymer (I) and, optionally at least one of componentsdescribed below,

-   -   a polyisocyanate compound (II),    -   a cellulose ester derivative (III) obtained by a ring-opening        graft polymerization of cyclic esters with a cellulose ester        having hydroxyl groups,    -   a modified vinyl-based copolymer (III′) not containing an        isocyanate group component which comprises copolymerization of        5-75% by mass of the cellulose ester derivative (III) with        25-95% by mass of other polymerizable unsaturated monomer (h)        (total of (III) and (h) is 100% by mass),    -   a graft copolymer (IV) which comprises copolymerization of 3-30%        by mass of a macromonomer (m) with 70-97% by mass of other        polymerizable unsaturated monomer (j) (total of (m) and (j) is        100% by mass), and,    -   a nonaqueous dispersed resin (V).

In the coating composition, the graft copolymer (I) is contained in notless than 50% by mass in the total resin solid components which arecomposed of the (I), (II), (III), (III′), (IV), and (V) which are 100%by mass.

Polyisocyanate compound (II) and oxazolidine compound (II′) As theabove-described curing agents, the polyisocyanate compound (II) andoxazolidine compound (II′) can be formulated in view of single-liquidtype.

As the polyisocyanate compound (II), there can be employed a lowmolecular weight isocyanate compound (d) having at least two isocyanategroups and a polymer (e) containing an unsaturated monomer havingisocyanate groups as a constructing unit.

As the low molecular weight compound (d), there are enumerated aliphaticisocyanates such as hexamethylene diisocyanate andtrimethylhexamethylene diisocyanate, cycloaliphatic isocyanates such asxylylene diisocyanate and isophorone diisocyanate, an adduct of thediisocyanates with polyvalent alcohols, a low molecular weight polyesterresin, and water, a polymer of the diisocyanates themselves (an adductof a diisocyanate monomer, there are enumerated Collonate L manufacturedby Nihon Polyurethane, Ltd. and Takenate D102 manufactured by TakedaPharmaceutical, Ltd.) and, further, an isocyanate buret compound, etc.

As the polymer (e) containing an unsaturated monomer having isocyanategroups, there is enumerated a copolymer containing isocyanate groupsobtained by copolymerization of the above-described monomer (f)containing an isocyanate group with other polymerizable unsaturatedmonomer (g) such as styrene and (meth)acrylates.

The above-described polyisocyanate compound (II) is formulated in arange of 0.5-40% by mass, and preferably 1-20% by mass based on totalsolid resinous components.

The above-described oxazolidine compound (II′) is formulated in a rangeof 0.5-5% by mass, and preferably 1-3% by mass based on total solidresinous components.

Cellulose Ester Derivative (III) and Modified Vinyl-Based Copolymer(III′)

In the coating composition of the present invention, there can beformulated the cellulose ester derivative (III) obtained by aring-opening graft polymerization of cyclic esters with a celluloseester having hydroxyl groups and the modified vinyl-based copolymer(III′) which comprises copolymerization of the cellulose esterderivative (III) with other polymerizable unsaturated monomer (g) from aviewpoint of an improvement of dryability.

As the cellulose ester derivative (III) obtained by a ring-opening graftpolymerization of cyclic esters with a cellulose ester having hydroxylgroups, there can be employed one (it may be not identical to thecellulose ester derivative (a)) which is mentioned in the illustrationof the cellulose ester derivative (a) component which becomes aconstructing unit in the above-described graft copolymer (I), and it isappropriately formulated in a range of 0.5-20% by mass based on totalresinous components Further, the modified vinyl-based copolymer (III′)is a graft copolymer not containing an isocyanate group component whichcomprises copolymerization of 5-75% by mass of the cellulose esterderivative-(III) described above (it may be not identical to thecellulose ester derivative (III) or the cellulose ester derivative (a))with 25-95% by mass of other polymerizable unsaturated monomer (g).

The other polymerizable unsaturated monomer (g) can be employed byappropriately selecting from the monomers (except the monomer (f)containing an isocyanate group and the monomer containing an activehydrogen (h)) which are stated in the illustration of the polymerizableunsaturated monomer (b) which becomes a constructing unit in theabove-described graft copolymer (I).

The modified vinyl-based copolymer (III′) is appropriately formulated ina range of 1-30% by mass based on total resinous components.

Graft Copolymer (IV)

Further, in the coating composition of the present invention, there maybe formulated a copolymer of ethylenic polymerizable monomers,particularly, the graft copolymer (IV) which comprises polymerization of3-30% by mass of a macromonomer (m) with 70-97% by mass of otherpolymerizable unsaturated monomer (j) from a viewpoint of an improvementof dryability.

The macromonomer is an oligomer or polymer having polymerizableunsaturated group at a terminal, it is prepared by conventionallypublicly-known methods, and there is preferred one having a glasstransition temperature of not less than 50° C. and a mass-averagemolecular weight of 1,000-25,000.

As the macromonomer, there is enumerated an oligomer or polymer such asa methacryloyl having methylmethacrylate or a methacryloyl havingbutylacrylate as a segment. As a commercially supplied product, thereare enumerated AA-2, AA-6, AB-2, and AB-6 which are manufactured by ToaGosei Chemicals, Ltd.

The other polymerizable unsaturated monomer (j) can be employed byappropriately selecting from the monomers (except the monomer containingan active hydrogen (h)) which are stated in the illustration of thepolymerizable unsaturated monomer (b) which becomes a constructing unitin the above-described graft copolymer (I). The graft copolymer (IV) isappropriately formulated in a range of 1-20% by mass based on totalresinous components.

Still further, in the coating composition of the present invention,there may be formulated the nonaqueous dispersed resin (V) from aviewpoint of an improvement of durability and dryability. The nonaqueousdispersed resin (V) is obtained by a polymerization of the monomer (g)under the presence of a dispersant in an organic liquid which candissolve the monomer (g) and does not substantially dissolve a polymerformed from the monomer (g) and, as the nonaqueous dispersed resin (V),there is preferred a dispersion liquid of a polymer particle having aglass transition temperature of 0-100° C. obtained by a polymerizationof a monomer appropriately selected from the other polymerizableunsaturated monomer (g) under the presence of a polymer (p) having amass-average molecular weight of 3,000-150,000.

As the polymer (p), there is enumerated a polymer or copolymer of a(meth)acrylate or styrene.

Concentration of the nonaqueous dispersed resin (V) is 10-60% by mass inthe dispersion liquid and the nonaqueous dispersed resin (V) is aresinous component in the dispersion liquid.

The nonaqueous dispersed resin (V) is appropriately formulated in arange of 0.5-50% by mass, preferably 1-30% by mass with respect to totalsolid resins.

The coating composition of the present invention primarily contains theabove-described graft copolymer (I), and the curing agents and resinouscomponents of the (II)-(V) are optionally formulated and, preferredstorage stability and physical properties of a coating layer areobtained by selecting a composition showing an isocyanate group contentof 0.5-28.5% by mass, preferably 3.0-15% by mass in total solid resinsas a whole of the composition.

In the coating composition of the present invention, there can beoptionally formulated pigments, solvents, ultraviolet ray absorbents,catalysts for curing, and dehydrating agents, etc. which are usualadditives for coatings.

The coating composition of the present invention can be employed as asingle-liquid coating which is capable of coating by adjusting alone toviscosity for coating with solvents for dilution.

As a coating method for the coating composition of the presentinvention, there can be utilized a conventionally publicly-known methodsuch as a spray coating, a brush coating, and a roller coating and, inusual, it is coated in thickness of the coating layer of 10-80 μm or so.

Hereinafter, No. IX of the present invention is illustrated in detail.

As a Lactide and lactone in the present invention, there are enumeratedones exemplified in the No. I of the present invention.

In the present invention, in the case of a ring-opening polymerizationof the above-described cyclic ester monomer, there is preferablyemployed a monomer having a moisture content of not more than 80 ppm andan acid value of not more than 0.12 mgKOH/g.

In the case of employing a monomer having more than the moisture contentand the acid value, it becomes difficult to control an averagecontinuous chain length in respective units, occasionally resulting inbeing incapable of attaining purpose of the present invention.

In the present invention, a compound having hydroxyl group is employedas an initiator. The compound may have a plurality of hydroxyl groups,and a plurality of the compounds may be even employed. Further, a metalalkoxide may be also employed as an initiator. As specific examples,there can be enumerated aluminum alkoxide, titanium alkoxide, zincalkoxide, tin alkoxide, zirconium alkoxide, yttrium alkoxide, samariumalkoxide, niobium alkoxide, neodymium alkoxide, and antimony alkoxide,etc.

As catalysts for the polymerization to be employed in the presentinvention, there can be enumerated metal compounds of aluminum,titanium, zinc, and tin without any limitation which are usuallyemployed. The compounds may be employed in combination of two or morekinds. Further, in the case that the metal alkoxide is employed as aninitiator, catalysts may be even not employed.

In the present invention, preferably, the average continuous chainlength is preferably not less than 3 in the lactide unit, and theaverage continuous chain length is preferably 1-10 in the lactone unit,and more preferably, the average continuous chain length is not lessthan 4.5 in the lactide unit, and the average continuous chain length is1.5-10 in the lactone unit. In the case of less than those, it becomesnot different from a random copolymer synthesized in a one step and, inthe case of more than those, it becomes not different from acompletely-blocked copolymer.

Further, in the present invention, preferably, the lactide unit ispreferably composed of a random portion having the average continuouschain length of not less than 5 and a block portion having the averagecontinuous chain length of less than 5. More preferably, the averagecontinuous chain length is not more than 3 in the random portion, andthe average continuous chain length is not less than 8 in the blockportion.

In the case that the average continuous chain length is not more thanthat in the random portion, it becomes not different from from acompletely-blocked copolymer and, in the case that the averagecontinuous chain length is less than that in the block portion, itbecomes not different a random copolymer synthesized in a one step.

The average continuous chain length of a random portion and blockportion in the lactone unit is identically mentioned.

In the present invention, a polymerization is conducted by addingresidual lactide during or after polymerization of 2-85% of the lactidein the total of the lactide and the lactone. In the case, conversion ispreferably not less than 80% in first step, and more preferably 80-97%.In the case that a monomer for second step is added at a conversionperiod being less than that, the average continuous chain length can notbe extended in the block portion, occasionally resulting in that purposeof the present invention cannot be attained.

Further, in the case that a monomer for second step is added at aconversion of not more than 90%, there is prepared a polymer having alarge amount of lactone units at terminals, and a thermal decompositionresistance is elevated.

In the case that the amount of lactide to be initially introduced isless than 2% based on total amount of lactide, it becomes not differentfrom a completely-blocked copolymer and, in exceeding 85%, it becomesnot different from a random copolymer synthesized in a one step.

Further, in the present invention, a polymerization is conducted byadding residual lactide and lactone during or after polymerization of2-85% of the lactide in the total lactide and 50-98% of the lactone inthe total lactone. In the case, a conversion is preferably not less than80% in first step, and more preferably 80-97%. In the case that amonomer for second step is added at a conversion period being less thanthat, the average continuous chain length can not be extended in theblock portion, occasionally resulting in that purpose of the presentinvention cannot be attained. Further, in the case that a monomer forsecond step is added at a conversion of not more than 90%, there isprepared a polymer having a large amount of lactone units at terminals,and a thermal decomposition resistance is elevated.

In the case that the amount of lactide to be firstly introduced is lessthan 2% based on total amount of lactide, it becomes not different froma completely-blocked copolymer and, in exceeding 85%, it becomes notdifferent from a random copolymer synthesized in a one step. In the casethat amount of lactone to be initially introduced is less than 50% basedon total amount of the lactone, it becomes not different from acompletely-blocked copolymer and, in exceeding 98%, it becomes identicalto the above-described invention.

Still further, in order to adjust the lactide/lactone to not more than2.5 in the present invention, there is repeatedly conducted an operationin which a polymerization is conducted by adding at least one kind ofthe residual lactide and lactone during or after polymerization of 2-85%of the lactide in the total lactide and 50-98% of the the lactone in thetotal lactone.

In the present invention, the copolymer is polymerized in two or moresteps. In the case of adding the monomers, a conversion in a previousstep is preferably not less than 80%. In the case of adding the monomersat a period of the conversion being less than that, the averagecontinuous chain length can not be extended in the block portion,occasionally resulting in that purpose of the present invention cannotbe attained.

Further, in the case that lactide and/or lactone are added at a secondstep from a final, final monomers are preferably added at a conversionof 80-97%. In the case, the average continuous chain length is extendedas desired in the block portion and, there is prepared a polymer havinga large amount of lactone units at terminals, and a thermaldecomposition resistance is elevated. The amount of lactide and lactoneto be initially introduced is the same as previously mentioned.

Still further, in the present invention, a polymerization is conductedby adding residual lactide and lactone during or after polymerization of25-90% of the lactone in the total lactone. In the case, conversion ispreferably not less than 80% in first step, and more preferably 80-97%.In the case that a monomer for second step is added at a conversionperiod being less than that, the average continuous chain length can notbe extended in the block portion, occasionally resulting in that purposeof the present invention cannot be attained. Further, in the case that amonomer for second step is added at a conversion of not more than 90%,there is prepared a polymer having a large amount of lactone units atterminals, and a thermal decomposition resistance is elevated. In thecase that the lactone in the first step is added at a period less than25% based on total amount of the lactone, the average continuous chainlength can not be extended in the block portion, occasionally resultingin that purpose of the present invention cannot be attained. Inexceeding 90%, it becomes not different from a completely-blockedcopolymer.

Still further, in the present invention, there is repeatedly conductedan operation in which a polymerization is conducted by adding at leastone kind of the residual lactide and lactone during or afterpolymerization of 25-90% of the the lactone in the total lactone. In thepresent invention, the copolymer is prepared using two or more steps. Inthe case of adding the monomers, conversion in a prior step ispreferably not less than 80%.

In the case that the monomers are added at a period of conversion lessthan that, the average continuous chain length can not be extended inthe block portion, occasionally resulting in that purpose of the presentinvention cannot be attained.

Still further, in the case that lactide and/or lactone are added at asecond step from a final, final monomers are preferably added at aconversion of 80-97%. In the case, the average continuous chain lengthis extended as desired in the block portion and, there is prepared apolymer having a large amount of lactone units at terminals, and athermal decomposition resistance is elevated.

The amount of lactone to be initially introduced is the same aspreviously mentioned.

In the present invention, reaction temperature and period areappropriately selected depending upon starting raw materials to beemployed, catalysts, a kind of initiators, and a copolymer to bedesired.

In the present invention, a cyclic ester monomer can bering-opening-polymerized by continuously feeding the cyclic estermonomer into a continuous polymerization apparatus.

As the continuous polymerization apparatus, there can be employed anagitator-equipped vessel type reactor, a plug-flow type reactor, and acombination thereof. More specifically, in addition to theagitator-equipped vessel type reactor, there can be employed a staticmixer type reactor, a column type reactor, and an extruder type reactor,etc. Further, these can be employed in combination of two or more kinds.

EXAMPLES

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited to those.

It is to be noted that “part” and “%” are shown by “part by mass” and “%by mass” except a case being specifically shown.

Hereinafter, Examples are illustrated in relation to an aliphaticpolyester of the No. I in the present invention and a method for thepreparation thereof.

A proportion occupied by an alcohol terminal and carboxylic acidterminal is merely shown by “%” based on total terminals of a polymerobtained.

Thermal decomposition was evaluated by a molecular weight retentionratio at the temperature of 180 and 200° C. and in a nitrogen atmosphereand air.

Hydrolizability was evaluated by a molecular weight retention ratio ofpellets after storing for a fixed period under a circumstance at thetemperature of 40° C. and humidity of 40% and a circumstance at thetemperature of 60° C. and humidity of 80%.

Evaluation of biodegradability was conducted using powder of a polymerobtained by a method using an active sludge according to JIS K6950.

Tensile test was conducted according to JIS K7113.

Comparative Example I-A

67.5 μl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 150 ppm and anacid value of 0.23 mg-KOH/g) to prepare a polycaprolactone at 180° C.,in which a proportion occupied by an alcohol terminal and a carboxylicterminal was 73% and 27%, respectively.

Number average molecular weight was 49,800 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 82% at 180° C. for 6 hours (under a nitrogen stream), 81%at 200° C. for 6 hours (under a nitrogen stream), 55% at 180° C. for 6hours (in air), and 42% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 84% at 40° C. for 360 hoursand 81% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 71% at a period after 25 days, and tensile strengthwas 252 kgf/cm².

Comparative Example I-B

67.5 μl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) to prepare a polycaprolactone at 180° C.,in which a proportion occupied by an alcohol terminal and a carboxylicterminal was 69% and 31%, respectively.

A result of a thermal decomposition test of the polycaprolactoneobtained was 88% at 180° C. for 6 hours (under a nitrogen stream), 87%at 200° C. for 6 hours (under a nitrogen stream), 60% at 180° C. for 6hours (in air), and 48% at 200° C. for 6 hours (in air), respectively.

Number average molecular weight was 64,000 in the polymer.

Further, in the hydrolizability test, it was 92% at 40° C. for 360 hoursand 91% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 72% at a period after 25 days, and tensile strengthwas 252 kgf/cm².

Example I-1

189.5 μl (1.2 mmol) of octanol (molecular weight of 130.23) which is aninitiator and 3.4 μl (8.4×10⁻³ mmol) of tin octylate which is a catalystwere added to 100 ml (902.4 mmol) of a caprolactone monomer (molecularweight of 114, water content of 50 ppm and an acid value of 0.10mg-KOH/g) to prepare a polycaprolactone at 180° C. and, in which aproportion occupied by an alcohol terminal and a carboxylic terminal was48% and 25%, respectively, and the remainder was an alkyl terminalderived from octanol.

Number average molecular weight was 70,400 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 82% at 180° C. for 6 hours (under a nitrogen stream), 95%at 200° C. for 6 hours (under a nitrogen stream), 95% at 180° C. for 6hours (in air), and 92% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 99% at 40° C. for 360 hoursand 98% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 59% at a period after 25 days, and tensile strengthwas 250 kgf/cm².

Example I-2

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) to conduct a polymerization at 180° C.,followed by allowing to react with 322.6 μl (2.1 mmol) of hexamethylenediisocyanate which is a modifier to prepare a polycaprolactone and, inwhich a proportion occupied by an alcohol terminal and a carboxylicterminal was 0% and 27%, respectively, and the remainder was an alkylterminal derived from octanol.

Number average molecular weight was 67,400 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 99% at 180° C. for 6 hours (under a nitrogen stream), 99%at 200° C. for 6 hours (under a nitrogen stream), 98% at 180° C. for 6hours (in air), and 98% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 99% at 40° C. for 360 hoursand 98% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 47% at a period after 25 days, and tensile strengthwas 260 kgf/cm².

Example I-3

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) to conduct a polymerization at 180° C.,followed by allowing to react with 86.2 μl (1.0 mmol) of butylene oxideand 322.6 μl (2.1 mmol) of hexamethylene diisocyanate which are amodifier to prepare a polycaprolactone and, in which a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0%,respectively.

Number average molecular weight was 63,800 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 102% at 180° C. for 6 hours (under a nitrogen stream), 102%at 200° C. for 6 hours (under a nitrogen stream), 100% at 180° C. for 6hours (in air), and 100% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 99% at 40° C. for 360 hoursand 98% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 38% at a period after 25 days, and tensile strengthwas 252 kgf/cm².

Example I-4

245.8 mg (1.2 mmol) of aluminum isopropoxide which is an initiator wasadded to 100 ml (902.4 mmol) of caprolactone monomer (water content of50 ppm and an acid value of 0.10 mg-KOH/g) to conduct a polymerizationat 180° C., followed by allowing to react with 86.2 μl (1.0 mmol) ofbutylene oxide and 322.6 μl (2.1 mmol) of hexamethylene diisocyanatewhich are a modifier to prepare a polycaprolactone and, in which aproportion occupied by an alcohol terminal and a carboxylic terminal was0%, respectively.

Number average molecular weight was 37,100 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 100% at 180° C. for 6 hours (under a nitrogen stream), 100%at 200° C. for 6 hours (under a nitrogen stream), 99% at 180° C. for 6hours (in air), and 99% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 99% at 40° C. for 360 hoursand 98% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from tat,degradation ratio according to the above evaluation method forbiodegradability was 45% at a period after 25 days, and tensile strengthwas 255 kgf/cm².

Comparative Example I-C

114.2 μl (1.2 mmol) of diethylene glycol which is an initiator and 3.4μl (8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50ml (451.2 mmol) of a caprolactone monomer (water content of 150 ppm andan acid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toprepare a (caprolactone/lactide) (50/50) block copolymer at 180° C., inwhich a proportion occupied by an alcohol terminal and a carboxylicterminal was 63% and 37%, respectively. It is to be noted that in thecase of a block copolymer, lactide was polymerized after polymerizationof caprolactone (hereinafter, in the case of a block copolymer, the samereaction order is applied).

Number average molecular weight was 76,400 in the polymer.

A result of a thermal decomposition test of samples was 50% at 180° C.for 6 hours (under a nitrogen stream), 33% at 200° C. for 6 hours (undera nitrogen stream), 31% at 180° C. for 6 hours (in air), and 25% at 200°C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 55% at 40° C. for 360 hoursand 48% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 58% at a period after 25 days, and tensile strengthwas 62 kgf/cm².

Example I-5

189.5 μl (1.2 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toprepare a (caprolactone/lactide) (50/50) block copolymer at 180° C. and,in which a proportion occupied by an alcohol terminal and a carboxylicterminal was 46% and 29%, respectively.

Number average molecular weight was 82,500 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 81% at 180° C. for 6 hours (under a nitrogen stream), 77%at 200° C. for 6 hours (under a nitrogen stream), 50% at 180° C. for 6hours (in air), and 29% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 77% at 40° C. for 360 hoursand 69% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 52% at a period after 25 days, and tensile strengthwas 63 kgf/cm².

Example I-6

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toconduct a polymerization at 180° C. and, followed by allowing to reactwith 322.6 μl (2.1 mmol) of hexamethylene diisocyanate which is amodifier to prepare a (caprolactone/lactide) (=50/50) block copolymerand, in which a proportion occupied by an alcohol terminal and acarboxylic terminal was 0% and 27%, respectively.

Number average molecular weight was 84,000 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 98% at 180° C. for 6 hours (under a nitrogen stream), 97%at 200° C. for 6 hours (under a nitrogen stream), 89% at 180° C. for 6hours (in air), and 79% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 82% at 40° C. for 360 hoursand 75% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 39% at a period after 25 days, and tensile strengthwas 62 kgf/cm².

Example I-7

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 65.0 g (451.2 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toconduct a polymerization at 180° C., followed by allowing to react with86.2 μl (1.0 mmol) of butylene oxide and 322.6 μl (2.1 mmol) ofhexamethylene diisocyanate which are a modifier to prepare a(caprolactone/lactide) (=50/50) block copolymer and, in which aproportion occupied by an alcohol terminal and a carboxylic terminal was0%, respectively.

Number average molecular weight was 84,200 in the polymer.

A result of a thermal decomposition test of the polycaprolactoneobtained was 99% at 180° C. for 6 hours (under a nitrogen stream), 99%at 200° C. for 6 hours (under a nitrogen stream), 98% at 180° C. for 6hours (in air), and 95% at 200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 98% at 40° C. for 360 hoursand 92% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 31% at a period after 25 days, and tensile strengthwas 65 kgf/cm².

Comparative Example I-D

67.5 μl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 40 ml(361.0 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toprepare a (caprolactone/lactide) (=40/60) random copolymer at 180° C.,in which a proportion occupied by an alcohol terminal and a carboxylicterminal was 72% and 28%, respectively.

Number average molecular weight was 87,700 in the polymer.

A result of a thermal decomposition test of samples was 89% at 180° C.for 6 hours (under a nitrogen stream), 85% at 200° C. for 6 hours (undera nitrogen stream), 85% at 180° C. for 6 hours (in air), and 85% at 200°C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 82% at 40° C. for 360 hoursand 76% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 77% at a period after 25 days, and tensile strengthwas 71 kgf/cm².

Example I-8

189.5 μl (1.2 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 40 ml(361.0 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of a lactidemonomer (water content of 70 ppm and an acid value of 0.12 mg-KOH/g) toprepare a (caprolactone/lactide) (=40/60) random copolymer at 180° C.,in which a proportion occupied by an alcohol terminal and a carboxylicterminal was 49% and 25%, respectively.

Number average molecular weight was 89,100 in the polymer.

A result of a thermal decomposition test of samples was 95% at 180° C.for 6 hours (under a nitrogen stream), 95% at 200° C. for 6 hours (undera nitrogen stream), 91% at 180° C. for 6 hours (in air), and 89% at 200°C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 92% at 40° C. for 360 hoursand 87% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 71% at a period after 25 days, and tensile strengthwas 73 kgf/cm².

Example I-9

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 40 ml(361.0 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) of lactide monomer(water content of 70 ppm and an acid value of 0.12 mg-KOH/g) to conducta polymerization, followed by allowing to react with 86.2 μl (1.0 mmol)of butylene oxide and 322.6 μl (2.1 mmol) of hexamethylene diisocyanatewhich are a modifier to obtain a (caprolactone/lactide) (=40/60) randomcopolymer at 180° C., in which a proportion occupied by an alcoholterminal and a carboxylic terminal was 0%, respectively.

Number average molecular weight was 89,900 in the polymer.

A result of a thermal decomposition test of samples was 100% at 180° C.for 6 hours (under a nitrogen stream), 98% at 200° C. for 6 hours (undera nitrogen stream), 101% at 180° C. for 6 hours (in air), and 97% at200° C. for 6 hours (in air), respectively.

Further, in the hydrolizability test, it was 98% at 40° C. for 360 hoursand 97% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 52% at a period after 25 days, and tensile strengthwas 73 kgf/cm².

Example I-10

411.5 μl (1.2 mmol) of titanium butoxide which is an initiator wereadded to 40 ml (361.0 mmol) of a caprolactone monomer (water content of50 ppm and an acid value of 0.10 mg-KOH/g) and 78.0 g (541.4 mmol) oflactide monomer (water content of 70 ppm and an acid value of 0.12mg-KOH/g) to conduct a polymerization at 180° C., followed by allowingto react with 86.2 μl (1.0 mmol) of butylene oxide and 322.6 μl (2.1mmol) of hexamethylene diisocyanate which are a modifier to obtain a(caprolactone/lactide) (=40/60) random copolymer, in which a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0%,respectively.

A result of a thermal decomposition test of samples was 98% at 180° C.for 6 hours (under a nitrogen stream), 98% at 200° C. for 6 hours (undera nitrogen stream), 92% at 180° C. for 6 hours (in air), and 91% at 200°C. for 6 hours (in air), respectively.

Number average molecular weight was 35,500 in the polymer.

Further, in the hydrolizability test, it was 94% at 40° C. for 360 hoursand 92% at 60° C. for 25 hours, respectively.

In a sheet having thickness of 75 μm compression-molded from that,degradation ratio according to the above evaluation method forbiodegradability was 54% at a period after 25 days, and tensile strengthwas 75 kgf/cm².

The above results are shown in Table I-1. TABLE I-1 Molecular weightretention OH acid ratio (%) Biodegradability Tensile terminal terminalThermal¹⁾ (degradation strength (%) (%) decomposition Hydrolysis²⁾ratio) (%) (kgf/cm²) Comparative 73 27 42 81 71 252 Example I-AComparative 69 31 48 91 72 252 Example I-B Example I-1 48 25 92 98 59250 Example I-2 0 27 98 98 47 260 Example I-3 0 0 100 98 38 252 ExampleI-4 0 0 99 98 45 255 Comparative 63 37 25 48 58 62 Example I-C ExampleI-5 46 29 29 69 52 63 Example I-6 0 27 79 75 35 62 Example I-7 0 0 95 9231 65 Comparative 72 28 85 76 77 71 Example I-D Example I-8 49 25 89 8771 73 Example I-9 0 0 97 97 52 73 Example I-10 0 0 91 92 54 75¹⁾Results of a thermal decomposition test at 200° C. for 6 hours (inair).²⁾Results of a hydrolysis test at 60° C. and humidity of 80% for 25hours.

Hereinafter, Examples are illustrated in relation to a particle-statecomposition for agriculture and gardening of the No. II in the presentinvention.

(1) Synthesis of an aliphatic polyester resin employed as a coating thinlayer II-A in which terminals are controlled or not controlled.

The following substances were employed as raw materials for thesynthesis.

Caprolactone monomer: molecular weight of 114, water content of 50 ppm(by mass), and an acid value of 0.10 mg-KOH/g.

Lactide monomer: molecular weight of 144, water content of 70 ppm (bymass), and an acid value of 0.12 mg-KOH/g.

Comparative Synthesis Example II-1 Synthesis of an Aliphatic PolyesterResin II-1 in which Terminals are not Controlled

67.5 μl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer to prepare a polycaprolactone at180° C., in which a proportion occupied by an alcohol terminal and acarboxylic terminal was 69% and 31%, respectively.

Synthesis Example II-1 Synthesis of an Aliphatic Polyester Resin II-1 inwhich Terminals are Controlled

189.5 μl (1.2 mmol) of octanol (molecular weight of 130.23) which is aninitiator and 3.4 μl (8.4×10⁻³ mmol) of tin octylate which is a catalystwere added to 100 ml (902.4 mmol) of a caprolactone monomer tosynthesize a polycaprolactone at 180° C., in which a proportion occupiedby an alcohol terminal and a carboxylic terminal was 48% and 25%,respectively, with respect to total terminals, and the remainder was analkyl terminal derived from octanol.

Synthesis Example II-2 Synthesis of an Aliphatic Polyester Resin II-2 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10-KOH/g) to polymerize at 180° C., followed by allowingto react with 322.6 μl (2.1 mmol) of hexamethylene diisocyanate whichare a modifier to obtain a polycaprolactone and, in which a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0% and27%, respectively.

Synthesis Example II-3 Synthesis of an Aliphatic Polyester Resin II-3 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer (water content of 50 ppm and anacid value of 0.10-KOH/g) to conduct a polymerization at 180° C.,followed by allowing to react with 86.2 μl (1.0 mmol) of butylene oxidewhich is a modifier to obtain a polycaprolactone and, in which aproportion occupied by an alcohol terminal and a carboxylic terminal was0%, respectively.

Synthesis Example II-4 Synthesis of an Aliphatic Polyester Resin II-4 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 100 ml(902.4 mmol) of a caprolactone monomer to conduct a polymerization at180° C., followed by allowing to react with 86.2 μl (1.0 mmol) ofbutylene oxide and 322.6 μl (2.1 mmol) of hexamethylene diisocyanatewhich are a modifier to obtain a polycaprolactone in which a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0%,respectively.

Comparative Synthesis Example II-2 Synthesis of an Aliphatic PolyesterResin II-2 in which Terminals are not Controlled

114.2 μl (1.2 mmol) of diethylene glycol which is an initiator and 3.4μl (8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50ml (451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of alactide monomer to synthesize at 180° C. In a block copolymer(polycaprolactone/lactide=50/50) obtained, a proportion occupied by analcohol terminal and a carboxylic terminal was 63% and 37%,respectively.

Synthesis Example II-5 Synthesis of an Aliphatic Polyester Resin II-5 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10¹³ mmol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of alactide monomer to synthesize a block copolymer(caprolactone/lactide=50/50) at 180° C. and, in which a proportionoccupied by an alcohol terminal and a carboxylic terminal was 46% and29%, respectively.

Synthesis Example II-6 Synthesis of an Aliphatic Polyester Resin II-6 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of alactide monomer to conduct a polymerization at 180° C., followed byallowing to react with 322.6 μl (2.1 mmol) of hexamethylene diisocyanatewhich are a modifier. In a block copolymer (caprolactone/lactide=50/50)obtained, a proportion occupied by an alcohol terminal and a carboxylicterminal was 0% and 27%, respectively.

Synthesis Example II-7 Synthesis of an Aliphatic Polyester Resin II-7 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mol) of tin octylate which is a catalyst were added to 50 ml(451.2 mmol) of a caprolactone monomer and 65.0 g (451.2 mmol) of alactide monomer to conduct a polymerization at 180° C., followed byallowing to react with 86.2 μl (1.0 mmol) of butylene oxide and 322.6 μl(2.1 mmol) of hexamethylene diisocyanate which are a modifier. In ablock copolymer (caprolactone/lactide=50/50) obtained, a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0%,respectively.

Comparative Synthesis Example II-3 Synthesis of an Aliphatic PolyesterResin II-3 in which Terminals are not Controlled

67.5 μl (1.2 mmol) of ethylene glycol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 40 ml(361.0 mmol) of a caprolactone monomer and 50 ml, 78.0 g (541.4 mmol) ofa lactide monomer to synthesize at 180° C. In a random copolymer(polycaprolactone/lactide=40/60) obtained, a proportion occupied by analcohol terminal and a carboxylic terminal was 72% and 28%,respectively.

Example II-8 Synthesis of an Aliphatic Polyester Resin II-8 in whichTerminals are Controlled

189.5 μl (1.2 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mmol) of tin octylate which is a catalyst were added to 40 ml(361.0 mmol) of a caprolactone monomer and 78.0 g (541.4 mmol) of alactide monomer to synthesize at 180° C. In a random copolymer(polycaprolactone/lactide=40/60) obtained, a proportion occupied by analcohol terminal and a carboxylic terminal was 49% and 25%,respectively.

Synthesis Example II-9 Synthesis of an Aliphatic Polyester Resin II-9 inwhich Terminals are Controlled

284.2 μl (1.8 mmol) of octanol which is an initiator and 3.4 μl(8.4×10⁻³ mol) of tin octylate which is a catalyst were added to 40 ml(451.2 mmol) of caprolactone monomer and 78.0 g (541.4 mmol) of alactide monomer to conduct a polymerization at 180° C., followed byallowing to react with 86.2 μl (1.0 mmol) of butylene oxide and 322.6 μl(2.1 mmol) of hexamethylene diisocyanate which are a modifier. In arandom copolymer (caprolactone/lactide=40/60) obtained, a proportionoccupied by an alcohol terminal and a carboxylic terminal was 0%,respectively.

Synthesis Example II-10 Synthesis of an Aliphatic Polyester Resin II-10in which Terminals are Controlled

411.5 μl (1.2 mmol) of titanium butoxide which is an initiator was addedto 40 ml (451.2 mmol) of a caprolactone monomer and 78.0 g (541.4 mmol)of a lactide monomer to conduct a polymerization at 180° C., followed byallowing to react with 86.2 μl (1.0 mmol) of butylene oxide which is amodifier. In a random copolymer (caprolactone/lactide=40/60) obtained, aproportion occupied by an alcohol terminal and a carboxylic terminal was0%, respectively.

(2) Method for the Preparation of a Particle-State Composition forAgriculture and Gardening, and an Apparatus

FIG. 7 shows an apparatus in a preferred embodiment of the presentinvention. Blowing column 1 has a column diameter of 200 mm, height of180 mm, diameter of an opening for blowing air of 42 mm, and which has ahole 2 for throwing a fertilizer and a hole 3 for exhausting a wastegas. Air for blowing is blown from a blower 10, and it reaches theblowing column through an orifice flow meter 9 and a heat exchanger 8.Flow volume is controlled at the flow meter 9, temperature is controlledat the heat exchanger 8, and waste gas is exhausted from the hole 3 forexhausting to an outside of the column.

A particle-state fertilizer to be supplied for coating is thrown fromthe hole 2 for throwing a fertilizer while streaming a fixed heat air toform a blowing stream. Treatment for coating is carried out by sprayingthe a solution containing a cellulose acetate composition having a lowsubstitution degree through a nozzle 4 for a liquid against the blowingstream after adjusting temperature of particles for coating to a fixedtemperature.

Preparation of a solution for coating is carried out while agitating inthe vicinity of a boiling point of solvent after supplying a fixedamount of a coating material and solvent into a liquid tank 11. Thesolution for coating is supplied into the nozzle 4 by a pump 5, andkeeping warmth is sufficiently conducted in order to maintain atemperature in a system.

After supplying the fixed solution for coating, the pump 5 is stopped,and then the blower 10 is stopped. Fertilizer coated is taken out of ahole 7 for taking out 6 is a valve.

In the FIG. 7, T₁, T₂, and T₃ are a thermometer, and SL is steam. It isto be noted that a particle-state fertilizer was coated while maintainthe following basic conditions in all Examples and Comparative Examples.

-   -   Nozzle for a liquid: opening of 0.8 mm, a Fullcon type    -   Amount of heated air: 4 m³/min    -   Temperature of heated air: 100° C.    -   Kind of fertilizer: Potassium-ammonium phosphate-nitrate having        5-7 meshes    -   Thrown amount of fertilizer: 5 kg    -   Concentration of a coating solution: Solid content of 5% by        weight    -   Feed amount of a coating solution: 0.5 kg/minute    -   Coating period: 10 minutes    -   Coating ratio (based on fertilizer): 5.5% by weight (containing        components of surfactants)    -   Solvent: Tetrahydrofran (THF)

Coating material II-A: There were employed materials obtained in theabove-described Synthesis Examples II-1 to II-10 and ComparativeSynthesis Examples II-1 to II-3.

Coating material II-B: Diacetate: manufactured by Daicel ChemicalIndustries, Ltd. [acetylated degree of 55.0 and viscosity of 100 cps in6%-acetone solution]

Coating material II-C: (additives to be added to the Coating materialII-A and Coating material II-B): talc

(3) Composition of a Coating Thin Layer and Biodegradability Test

Two sides were cut in relation to every particle of 50 particles ofcoated samples prepared in the Examples and Comparative Examples, andthen those were immersed in water to remove internal fertilizingcomponents. After drying, those were finely crushed, and decompositionratio was measured according to JIS K6950 (an experimental method forbiodegradability under airing by an active sludge). Active sludgeemployed was an active sludge sent from a municipal drainage in Himejicity.

Examples II-1 to II-14 and Comparative Example II-1 to II-3

Coated phosphorous potassium ammonium nitrate having a variety ofcomposition in a coating layer was prepared by the above-describedmethod for the preparation using coating materials II-A, II-B, and II-Cat a proportion shown in Table II-1.

Table II-1 shows results of composition ratio in coating layer andbiodegradability in the Examples II-1 to II-14 and Comparative ExamplesII-1 to II-3.

In the case of employing the coating materials II-A, II-B, II-C, asunderstood from comparison of the Comparative Example II-1 with ExamplesII-1, II-3, II-5, and II-7, biodegradation rate was able to besignificantly lowered over a wide range in Examples II-1, II-3, II-5,and II-7 compared to Comparative Example II-1.

Also in the case of employing the coating materials II-A and II-C, asunderstood from comparison of the Comparative Example II-2 with ExamplesII-4, II-6, and II-8, biodegradation rate was able to be significantlylowered over a wide range in Examples II-2, II-4, II-6, and II-8compared to Comparative Example II-2.

Further, also in the case of adding II-B and II-C using the randomcopolymer (caprolactone/lactide=40/60 or 50/50) as the coating materialII-A, as understood from comparison of the Comparative Example II-3 withExamples II-9, II-10, and II-11, and from comparison of the ComparativeExample II-4 with Examples II-12, II-13, and II-14, biodegradation ratewas able to be significantly lowered over a wide range by the presentinvention. TABLE II-1 Composition of coating layer materialBiodegradation Coating layer material II- Coating layer Coating layerratio after 28 A % material II-B % material II-C % Solvent daysComparative Example II-1 Comparative synthesis Diacetate 20 Talc 50 THF60 Example II-1 30 Comparative Example II-2 Comparative synthesis None 0Talc 50 THF 80 Example II-1 50 Example II-1 Synthesis Example II-1 30Diacetate 20 Talc 50 THF 40 Example II-2 Synthesis Example II-1 50 None0 Talc 50 THF 65 Example II-3 Synthesis Example II-2 30 Diacetate 20Talc 50 THF 35 Example II-4 Synthesis Example II-2 50 None 0 Talc 50 THF60 Example II-5 Synthesis Example II-3 30 Diasetate 20 Talc 50 THF 30Example II-6 Synthesis Example II-3 50 None 0 Talc 50 THF 50 ExampleII-7 Synthesis Example II-4 30 Diacetate 20 Talc 50 THF 30 Example II-8Synthesis Example II-4 50 None 0 Talc 50 THF 45 Comparative Example II-3Comparative synthesis Diacetate 20 Talc 50 THF 50 Example II-2 30Example II-9 Synthesis Example II-5 30 Diacetate 20 Talc 50 THF 40Example II-10 Synthesis Example II-6 30 Diacetate 20 Talc 50 THF 30Example II-11 Synthesis Example II-7 30 Diacetate 20 Talc 50 THF 20Comparative Example II-4 Comparative synthesis Diacetate 20 Talc 50 THF65 Example II-3 30 Example II-12 Synthesis Example II-8 30 Diacetate 20Talc 50 THF 50 Example II-13 Synthesis Example II-9 30 Diacetate 20 Talc50 THF 40 Example II-14 Synthesis Example II-10 30 Diacetate 20 Talc 50THF 40

Hereinafter, there is illustrated Examples in relation to theparticle-state fertilizer for agriculture and gardening of the presentinvention.

(1) Synthesis of a Cyclic Ester-Modified Cellulose Ester

A sufficiently-dried reaction vessel equipped with an agitator, athermometer, and a condenser was charged with 50 parts ofε-caprolactone, 50 parts of a sufficiently-dried cellulose acetate (anacetylated degree of 55.2% and a substitution degree of 2.43manufactured by Daicel Chemical Industries, Ltd.) at 180° C. whileagitating and, after uniformly dissolved, 0.12 part of tin octylate wascharged, followed by allowing to react for 3 hours.

Thus, a caprolactone-modified cellulose acetate [I] was obtained whichis slightly yellow and transparent. Intrinsic viscosity of [η]=0.75liter/g in a graft polymer was measured using acetone at 50° C.

The caprolactone-modified cellulose acetate [I] obtained was employed asthe coating material III-A

(2) A Method for the Preparation of a Particle-State Fertilizer forAgriculture and Gardening and an Apparatus

It was prepared by a method for the preparation in an Example of the No.II of the present invention using an apparatus of the FIG. 7.

Herein, ethyl acetate or 2-butanone was employed as a solvent.

Coating Material III-B

PCL: a polycaprolactone [PCL-H7] manufactured by Daicel ChemicalIndustries, Ltd.

Diacetate: It was manufactured by Daicel Chemical Industries, Ltd.[acetylated degree of 55.0 and viscosity of 100 cps in 6%-acetonesolution].

Coating material III-C (fillers for adding to the coating material III-Aand the coating material III-B): talc

(3) Composition of a Coating Thin Layer and Biodegradability Test

By the above-described method for the preparation, a coated phosphoricpotassium ammonium nitrate having a variety of composition shown inTable III-1. After that, two sides were cut in relation to everyparticle of 50 particles of coated samples prepared in the Examples, andthen those were immersed in water to remove internal fertilizingcomponents. After drying, those were finely crushed, and decompositionratio was measured according to JIS K6950 (a biodegradabilityexperimental method under airing by an active sludge). Active sludgeemployed was an active sludge sent from a municipal drainage in Himejicity.

Table III-1 shows results of Examples III-1 to III-6. TABLE III-1Composition of coating layer material Coating Coating Coating layerlayer layer Biodegradation material material material ratio after 28III-A % III-B % III-C % Solvent days Example [1] 50 None 0 Talc 50 Ethyl60 III-1 acetate Example [1] 50 None 0 Talc 50 2- 60 III-2 butanoneExample [1] 30 PCL 20 Talc 50 Ethyl 80 III-3 acetate Example [1] 30 PCL20 Talc 50 2- 80 III-4 butanone Example [1] 30 Diacetate Talc 50 Ethyl40 III-5 20 acetate Example [1] 30 Diacetate Talc 50 2- 40 III-6 20butanone

Hereinafter, there are illustrated Examples in relation to a base filmfor the marking film of the No. IV of the present invention.

Examples IV-1 to IV-4

A reaction vessel equipped with an agitator and a thermometer, acondenser (equipped with a drying tube at a top portion) was chargedwith an absolutely-dried cellulose acetate (an acetylated degree of 55%and a substitution degree of 2.45 manufactured by Daicel ChemicalIndustries, Ltd., referred to as CA in Table) and a refinedc-caprolactone, and respective part by mass is shown in Table IV-1described below, followed by uniformly dissolving the cellulose acetateby agitating while heating at 180° C. and adjusting moisture content ina reaction system to not more than 0.1% by mass.

After confirming a condition of uniformly dissolving, 0.24 part by massof tin (II) octylate was added dropwise as a catalyst to allow to reactfor 4 hours, followed by taking out a graft product from the reactionvessel. The product was dried by hot air at 90° C. for 8 hours, followedby melting at 230° C. using an injection machine to prepare test piecesfor evaluation of physical properties. Evaluation was conducted bymeasurements of tensile properties and a bleed out property according tomethods described below, and by visual observation of the presence orabsence of a migration of components other than the cellulose acetate.

Tables IV-2 (1) and (2) show results of the evaluations.

(1) Presence or absence of a migration of components other than thecellulose acetate: Observation of the presence or absence of adherenceof respective components in surface of a molded article.

(2) Bleed out test: There was measured a mass decrease degree in amolded article having a square of 5 cm×5 cm molded by injectionaccording to measurement conditions described below.

(a) Test by a hot air circulating dryer: 80° C.×1 day or 4 days.

(b) Tensile test: according to JIS K7113.

Comparative Examples IV-1 to IV-2

Composition containing respective plasticizers was prepared by mixing100 parts by mass of the absolutely-dried cellulose acetate (anacetylated degree of 55% and a substitution degree of 2.45 manufacturedby Daicel Chemical Industries, Ltd., referred to as CA in the TableIV-1) with 40 parts by mass of diethylphthalate (DEP) (ComparativeExample IV-1) and 40 parts by mass of Cellgreen™ 3058 (athree-functional lactone polyol having a molecular weight of 500manufactured by Daicel Chemical Industries, Ltd.) (Comparative ExampleIV-2) which are a plasticizer, followed by drying by hot air at 50° C.for 12 hours. After that, the composition was melted at 230° C. using aninjection machine to likewise prepare test pieces as in the Examples.Respective evaluations were conducted by measurements of tensileproperties and a bleed out property, and by visual observation of thepresence or absence of a migration of components such as plasticizersother than cellulose acetate. Table IV-1 shows the composition, andTables IV-2 (1) and (2) show results of the respective evaluations.TABLE IV-1 Raw materials and feed- Raw materials and feed- ing ratio(part by mass) Com- ing ratio (part by mass) Exam- Cellulose ε    −parative Cellulose ple acetate caprolactone Example acetate PlasticizerIV-1 100 50 IV-1 100 40 (DEP) IV-2 100 100 IV-3 100 150 IV-2 100 40(Lactone IV-4 100 200 polymer)

TABLE IV-2 (1) Comparative Tensile Example Example properties IV-1 IV-2IV-3 IV-4 IV-1 IV-2 Yield strength 480 320 120 60 270 310 (kgf/cm²)Yield 6.1 4.8 7.2 7.3 5.1 5.5 extension (%) Fracture 500 340 210 120 260400 strength (kgf/cm²) Fracture 28 52 74 120 43 65 extension (%)Elasticity 17500 13800 4200 2200 6800 11900 (kgf/cm²)

TABLE IV-2 (2) Bleed out properties Comparative (heated air-circulatingExample Example dryer test) IV-1 IV-2 IV-3 IV-4 IV-1 IV-2 (1 day) Totalweight retention 99.9 99.8 99.6 99.4 97.2 96.8 ratio (%) Weightretention ratio 99.7 99.6 99.3 99.1 90.2 88.7 of plasticizer (%) (4days) Total weight retention 99.8 99.7 99.4 99.2 97.1 96.6 ratio (%)Weight retention ratio 99.4 99.4 99.0 98.8 89.9 88.0 of plasticizer (%)Presence or absence of None None None None None None movement ofcompoments other than cellulose acetate

Hereinafter, there are specifically illustrated Examples in relation tothe heat-sensitive transfer recording material and method for thepreparation thereof of the No. V in the present invention.

Evaluation methods are as follows.

(Evaluation of Concentration in a Printing Picture Image):

A picture image recording material (a picture image recording sheet) wasprinted using a sublimatable type digital color printer DPP-M1(manufactured by Sony Ltd.) to measure a coloring concentration with areflection type Macbeth densitometer RD-1255 (manufactured by SakataInks, Ltd.). It is to be noted that an exclusive printer pack VPM-P50STAfor DPP-M1 was employed as an ink ribbon. Printing conditions werefitted to a standard setting up for a printer driver (manufactured bySony Ltd.) for a Mackintosh (manufactured by Apple Ltd.).

(Evaluation of Strippability):

There was visually observed the presence or absence of occurrence of anabnormal transfer by thermal fusion when an ink ribbon is stripped froma picture image recording sheet in printing.

Example V-1

(Polymerization of a Graft Polymer)

A sufficiently-dried reaction vessel equipped with an agitator and athermometer, a condenser was charged with 50 parts of ε-caprolactone and100 parts of a sufficiently-dried cellulose acetate (an acetylateddegree of 55.2% and a substitution degree of 2.43 manufactured by DaicelChemical Industries, Ltd.) at 180° C. while agitating and, afteruniformly dissolved, 0.12 part of tin octylate was charged, followed byallowing to react for 3 hours.

Thus, a graft polymer was obtained which is slightly yellow andtransparent. Intrinsic viscosity of [η]=0.75 dl/g in the graft polymerwas measured using acetone at 50° C.

(Preparation of a Sublimatable Transfer Picture Image Recording Sheet)

20 parts of the graft polymer was dissolved in 80 parts of acetone toprepare a solution, and the solution was coated on a polypropylene-basedsynthetic paper (Yupo FPG-150 manufactured by Ohji Yuka Goseishi, Ltd.)having thickness of 150 μm using a wire bar so that a dried coatinglayer is obtained which has thickness of 10 μm, followed by drying at110° C. for 10 minutes to obtain a heat-sensitive transfer imagerecording material having a dye-receiving layer.

As results in evaluation of a print recording image concentration, therewas obtained a high coloring concentration of 5.5 (total sum of amaximum value of reflection concentration in respective colors includingcyan, magenta, yellow, and black).

Further, a high strippability was visually observed without causing anabnormal transfer by thermal fusion.

Example V-2

The same polymerization was conducted as in the Example V-1 by changinga feeding amount of ε-caprolactone to 70 parts.

Intrinsic viscosity of [η]=0.52 dl/g in a graft polymer obtained wasmeasured using acetone at 50° C. A picture image recording sheet wasprepared by the same method as in the Example V-1 using graft polymerobtained. As results of the same test as in the Example V-1, there wasobtained a high coloring concentration of 5.5. Further, a highstrippability was visually observed without causing an abnormal transferby thermal fusion.

Hereinafter, Examples are specifically illustrated in relation to aheat-sensitive transfer image recording material of the No. VI in thepresent invention.

(1) Sticking Resistance

It was evaluated using a sublimating-type printer or a line-type printershown hereinafter.

(A-1): A melting type printer: Printing was conducted at a speed of2″/sec in a printing energy of 25 mJ/mm² using TECB-30 (manufactured byTokyo Denki, Ltd.). (A-2): A melting type printer: Printing wasconducted at a speed of 7″/sec in a printing energy of 23 mJ/mm² usingSWEDOT 196 (manufactured by UBI, Ltd.). (B): A sublimating type printer:Transfer printing was conducted at an applied voltage of 14V using aSharp Color video printer GZ-P11. ⊚: Sticking is not completelyobserved, and transport can be stably conducted. ∞: Sticking is notalmost caused. Δ: Sticking is slightly caused. x: Sticking isremarkable, and transport can not be conducted at all.

(2) Blocking Resistance

1) After laminating an ink layer with a heat-resistible protectinglayer, it was placed at 40° C. for 72 hours under compression of 392.3kPa (4.0 kgf/cm²), and there was observed an extent of transfer of anink layer to the heat-resistible protecting layer when being stripped.

2) After laminating an ink layer with a heat-resistible protectinglayer, it was placed at 50° C. for 72 hours under compression of 392.3kPa (4.0 kgf/cm²), and there was observed an extent of transfer of anink layer to the heat-resistible protecting layer when being stripped.◯: Transfer by blocking is not observed at all. Δ: Transfer by blockingis slightly observed. x: Transfer is distinctly observed.

(3) Migrating Property of a Heat-Resistible Protecting Layer to an InkLayer

After laminating an ink layer with a heat-resistible protecting layer,it was placed at room temperatures for 72 hours under compression of392.3 kPa (4.0 kgf/cm²), and evaluation was conducted using asublimating-type printer or a line-type printer shown hereinafter. (A):A melting type printer: Printing was conducted at a standard transferenergy (approximately 17 mJ/mm²) in Intermec 8646, followed by comparingto a picture image obtained as in the above without bringing intocontact with the heat-resistible protecting layer. (B): A sublimatingtype printer: Transfer print was conducted at an applied voltage of 12Vusing a Sharp Color video printer GZ-P11, followed by comparing to apicture image obtained as in the above without bringing into contactwith the heat-resistible protecting layer. ◯: Quite same image isobtained. Δ: There were slightly observed lack of an image andunevenness of transfer. x: Lack of an image and unevenness of transferare remarkable.

(3) Staining Property of a Thermal Head

Using a printer shown below, transfer of 500 m was continuouslyconducted, and staining in a thermal head was observed. Further, aquality of initial printing was compared to a quality of final printing.(A-1): A melting type printer: Printing was conducted at a speed of4″/sec in a printing energy of 20 mJ/mm² using TECB-30 (manufactured byTokyo Denki, Ltd.). (A-2): A melting type printer: Printing wasconducted at a speed of 7″/sec in a printing energy of 22 mJ/mm² usingSWEDOT 196 (manufactured by UBI, Ltd.). (B): A sublimating type printer:Transfer print was conducted at an applied voltage of 12V using a SharpColor video printer GZ-P11. ≈: Staining is not completely observed in athermal head. Δ: Sticking is slightly caused, and quality of printingslightly lowers. x: Staining is remarkable, and quality of printingremarkably lowers.

(3) Heat Sensitivity

It was confirmed by capability of obtaining a picture image withoutsticking using a high speed printer (A-2) in the sticking resistancetest.

Preparation Example VI-1

A sufficiently-dried reaction vessel equipped with an agitator and athermometer, a condenser was charged with 50 parts of ε-caprolactone and100 parts of a sufficiently-dried cellulose acetate (an acetylateddegree of 55.2% and a substitution degree of 2.43 manufactured by DaicelChemical Industries, Ltd.) at 180° C. while agitating under anatmosphere of dried nitrogen and, after uniformly dissolved, 0.12 partof tin octylate was charged, followed by allowing to react for 3 hours.Thus, a graft polymer was obtained which is slightly yellow andtransparent.

Intrinsic viscosity of [η]=0.75 dl/g in a graft polymer was measuredusing acetone at 50° C. This is designated as Resin A.

Preparation Example VI-2

A sufficiently-dried reaction vessel equipped with an agitator and athermometer, a condenser was charged with 70 parts of ε-caprolactone,100 parts of a sufficiently-dried cellulose acetate (an acetylateddegree of 55.2% and a substitution degree of 2.43 manufactured by DaicelChemical Industries, Ltd.) at 180° C. while agitating under anatmosphere of dried nitrogen and, after uniformly dissolved, 0.12 partof tin octylate was charged, followed by allowing to react for 3 hours.Thus, a graft polymer was obtained which is slightly yellow andtransparent. Intrinsic viscosity of [η]=0.50 dl/g in a graft polymer wasmeasured using acetone at 50° C. This is designated as Resin B.

Example VI-1

Methyl ethyl ketone/cyclohexanone (9/1) solution containing 4% of theResin A obtained in the Preparation Example VI-1 was coated on lowersurface of a polyethylene terephthalate (PET) film having thickness ofapproximately 4.5 μm with a wire-bar, and dried at 90° C. for 30 secondsto form a heat-resistible protecting layer having thickness ofapproximately 0.5 μm. Further, a dispersion liquid of a melting-typeheat-transfer ink (a) described below was coated on upper surface of thefilm, and dried to prepare an ink layer having a coating amount ofapproximately 2.8 g/cm² and obtain a heat-transfer recording medium.

Melting-Type Heat-Transfer Ink (a) carnauba wax 6 parts paraffin wax 8parts carbon black 4 parts toluene 82 parts

Example VI-2

Methyl ethyl ketone/cyclohexanone (9/1) solution containing 5% of theResin B obtained in the Preparation Example VI-2 was coated on lowersurface of a PET film having thickness of approximately 4.5 μm with awire-bar, and dried at 90° C. for 30 seconds to form a heat-resistibleprotecting layer having thickness of approximately 0.5 μm. Further, anink layer was likewise formed as in the Example VI-1 on upper surface ofthe film to obtain a heat-transfer recording medium.

Example VI-3

Methyl ethyl ketone/cyclohexanone (9/1) solution containing 5% of theResin A obtained in the Preparation Example VI-1 was coated on lowersurface of a PET film having thickness of approximately 4.5 μm with awire-bar, and dried at 90° C. for 30 seconds to form a heat-resistibleprotecting layer having thickness of approximately 0.5 μm. Further, adispersion liquid of a sublimating-type heat-transfer ink (b) describedbelow was coated on upper surface of the film, and dried to prepare anink layer having a coating amount of approximately 0.8 g/cm² and obtaina heat-transfer recording medium.

Sublimating-Type Heat-Transfer Ink (b) MS Red G 6 parts polyvinylbutylal 8 parts 1,4-dioxane 55 parts toluene 17 parts methylethyl ketone17 parts

Example VI-4

Methyl ethyl ketone/cyclohexanone (9/1) solution containing 7% of theResin B obtained in the Preparation Example VI-2 was coated on lowersurface of a PET film having thickness of approximately 6.0 μm with awire-bar, and dried at 90° C. for 30 seconds to form a heat-resistibleprotecting layer having thickness of approximately 0.6 μm. Further, anink layer was likewise formed as in the Example VI-1 on upper surface ofthe film to obtain a heat-transfer recording medium.

Printing was conducted in relation to the heat-transfer recordingmediums obtained in the respective Examples, and there were compared asticking property, a blocking property, a migrating property of theheat-resistible protecting layer to the ink layer, staining resistanceand heat sensitivity of a thermal head. Results are shown in Table VI-1.TABLE VI-1 Example VI-1 VI-2 VI-3 VI-4 Sticking resistance A-1 ⊚ ⊚ — —A-2 ⊚ ⊚ — — B — — ⊚ ⊚ Blocking resistance 1 ◯ ◯ ◯ ◯ 2 ◯ ◯ ◯ ◯ Movementonto ink layer A ◯ ◯ — — B — — ◯ ◯ Staining property of a thermal headA-1 ◯ ◯ — — A-2 ◯ ◯ — — B — — ◯ ◯

From the results in the Table VI-1, it is understood that theheat-transfer recording medium of the present invention is excellent ina sticking property and it is excellent in a blocking property, amigrating property of the heat-resistible protecting layer to the inklayer, and a staining resistance of a thermal head.

Hereinafter, the conductive coating composition of the No. VII in thepresent invention is more specifically illustrated by SyntheticExamples, Examples, and Comparative Examples.

Synthetic Examples VII-1 and VII-2 Synthesis of a Cellulose EsterDerivative

A reaction vessel equipped with an agitator and a thermometer, acondenser (equipped with a drying tube at a top portion) was chargedwith an absolutely-dried cellulose acetate (an acetylated degree of 55%and a substitution degree of 2.45 manufactured by Daicel ChemicalIndustries, Ltd., and it is described as CA in the Table VII-1) and arefined c-caprolactone in a mass ratio shown in the Table VII-1,whereby, moisture content in a reaction system is controlled to not morethan 0.1%, followed by heating at 180° C. while agitating to uniformlydissolve the cellulose acetate. After confirming dissolving, 0.24 partof tin octylate (II valent) was charged, followed by allowing to reactfor 4 hours and take out a graft product from the reaction vessel. TABLEVII-1 Synthesis Feed (part) Mass average Example Cellulose acetateε-caprolactone molecular weight VII-1 100 50 150,000 VII-2 100 100180,000

Examples VII-1 to VII-3 and Comparative Examples VII-1 to VII-5Synthesis Examples of Coatings A to H

The coatings A to H were prepared by formulation shown in Table VII-2.TABLE VII-2 Example Comparative Example VII-1 VII-2 VII-3 VII-1 VII-2VII-3 VII-4 VII-5 Coating A B C D E F G H Resin 20% 360 400 335 310 450sparklon S-822 70% oil - 77 77 85 free polyester Uban 222 35 35 42.5Synthesis 8 8 6 10 Example VII-1 Synthesis 5 5 5 Example VII-2Conductive Denka HS- 10 10 25 30 pigment 100 Vulcan XC- 10 10 72Graphite 10 8 10 15 powder POG-2 Graphite 8 powder SP- 10 Zinc oxide 150JR-600A 10 10 10 Solvent Toluene 100 100 100 Ethyl 40 50 50 40 40 40 40acetate Total 428 295 295 460 408 386 297.5 610

Values in the Table are represented by part by mass.

Sparklon S-822: a trade name of a chlorinated polyolefin manufactured byNippon Seishi, Ltd., a toluene solution having a solid content of 20%.

Oil-free polyester: isophthalic acid/tetrahydrophthalicacid/trimeyhlolpropane/neopentyl glycol, a xylene solution having asolid content of 70% (OH value of 50 mg KOH/g of a resin, an acid valueof 9 mg KOH/g of a resin).

Uban 222: a trade name of a urea melamine resin manufactured by MitsuiKagaku, Ltd., a n-butanol solution having a solid content of 60%.

Denka HS-100: a trade name of a conductive carbon black (DBP absorptionamount of 115 ml/100 g, electric resistivity of 0.24 Ω·cm) manufacturedby Denki Kagaku Kogyo, Ltd.

Vulcan XC-72: a trade name of a conductive carbon black (DBP absorptionamount of 175 ml/100 g, electric resistivity of not more than 0.1 Ω·cm)manufactured by Cabot. Corp. Ltd.

Scaly graphite (graphite powder) POG-2: a trade name of an artificialgraphite (an average particle diameter of 2 μm) manufactured by KyowaCarbon. Ltd.

Scaly graphite (graphite powder) SP-5: a trade name of a graphite (anaverage particle diameter of 45 μm) manufactured by Nihon Kokuen Kogyo.Ltd.

JP-600A: a trade name of a titanium white manufactured by Teikoku Kako.Ltd.

(Preparation of a Test Plate)

Material “a” (a polypropylene plate manufactured by Mitsubishi Yuka,Ltd.) and Material “b” (a RIM-polyurethane plate manufactured by NihonTest Panel, Ltd.) which are adjusted to the size of 70×150×3 mm wereexposed in trichloroethane vapor for 1 minute to remove grease.Subsequently, the above-described coatings A-H were coated on the platesby spray coating so that the thickness of a dried coating layer isadjusted to 20 μm, followed by drying by conditions as shown in TableVII-3. Subsequently, a finishing coating (Soflex #1200 white: an aminopolyester-based resin coating manufactured by Kansai Paint, Ltd.) wascoated at coating conditions of a rotation speed of 15000 rpm and ashaving pressure of 1 kg/cm², applied voltage of 90 kV, a distance of 30cm between an article to be coated and a top of a spray gun, adischarging amount of 200 ml/min, a conveyer speed of 3 m/min using anelectrostatic coating machine (Turbo G minibel), followed by drying at120° C. for 30 minutes to supply to tests.

Results of evaluation tests are shown in Table VII-3. TABLE VII-3Product by the present Product corresponding to Comparative inventionExamples Kind of coating A B B C D E E F G H Storage stability ofcoating (1) ◯ ◯ ◯ ◯ ◯ Δ Δ Δ ◯ X Resistivity Material a b b b a a a a b aof coating Dry-  20° C.  3 2 × 10⁸ 2 × 10⁹ 1.5 × 10⁸ layer ing 80% RHminutes (Ω/cm) (2) condi-  6 3 × 10⁶ 3 × 10⁷ 1.5 × 2 × 10⁸ tions minutes 10⁸ 120° C. 10 7 × 10⁴ 5.5 × 10⁴ 2.5 × 10⁶ minutes Coated ratio of afinishing coating (%) (3) 98 98 100 100 32 73 86 99 100 40 GeneralFinish- Visual outer appearance (4) ◯ ◯ ◯ ◯ X Δ Δ ◯ ◯ X coating ing 60°mirror reflection ratio 93 94 93 93 76 89 91 93 92 80 proper- property(%) ties Brightness (5) 82 78 84 86 14 36 65 78 81 25 property Adhesion(6) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ X ◯ of Bending resistance (7) ◯ ◯ ◯ ◯ ◯ X X X ◯ Xcoating Chipping resistance (8) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ X Δ Moisture resistance(9) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ

Tests methods for evaluation and results in Table VII-3 are shown asfollows.

(1) Storage stability of coatings: Coatings were charged into apolyethylene-made closed vessel and placed at 40° C. for 1 month,followed by confirming the presence or the absence of abnormality suchas a deposition state of pigments and a viscosity change to evaluate bya level of ◯ to x.

◯: none of abnormality, Δ: pigments deposited, and x: pigmentsremarkably deposited and viscosity remarkably increased.

(2) Resistivity of a coating layer: Layers having resistivity of coatinglayer of less than 1×10⁸ Ω/cm were measured using a Rolestar MCP-tester(manufactured by Mitsubishi Yuka, Ltd.). Layers having resistivity ofcoating layer of not less than 1×10⁸ Ω/cm were measured using anelectric cell-style ohm-meter Hioki 3110 (manufactured by Hioki Denki,Ltd.).

(3) Coated ratio: A tin plate having the same size as in the material“a” and the material “b” was employed in the preparation of test plates,and a finishing coating was conducted on the tin plate and driedtogether with plates in which the material “a” and the material “b” arecoated using the coatings A-H by the same method as in the preparationof the above-described test pieces. Coated ratio was calculated by theequation described below.(the weight of the finishing coating adhered to the material “a” and thematerial “b”/the weight of the finishing coating adhered to the tinplate)×100

(4) Visual outer appearance: The presence or the absence of glossiness,smoothness, and abnormality in the coating layer was judged by a levelof ◯ to x under conditions of not more than 500 lux by a color matchingfluorescent lamp at an inside of a room.

-   -   ◯: none of abnormality, Δ: slightly poor, x: poor

(5). Brightness: It was measured using Image Clarity Meter (HA-ICHmanufactured by Suga Shikenki, Ltd.)

(6) Adhesion: It was evaluated by a crosshatched test by a level of ◯and x using a cellophane tape according to JIS K5400.

-   -   ◯: none of peeling, x: peeled at all surface

(7) Bending resistance: Test plate was cut into a size of 20×150 mm, andbent at 180° by winding around a column (made by a steel) havingdiameter of 25.4 mm by facing coating surface to outside under anatmosphere of −20° C. and, an extent of peeling and crack in the coatinglayer was evaluated by a level of ◯ to x.

-   -   ◯: nothing of abnormality, Δ: slightly cracked, x: cracked and        peeled        (8) Chipping Resistance:

-   (i) Tester: Q-G-R gravelometer (manufactured by Q Panel, Co.)

-   (ii) Stones sprayed: crushed stone having diameter of approximately    15-20 mm

-   (iii) amount of stones sprayed: approximately 500 ml

-   (iv) air pressure in spraying: approximately 4 kg/cm²

-   (v) temperature in test: approximately −20° C.

Test piece was clamped at a stand for test pieces, and approximately 500ml of crushed stones were sprayed toward test pieces by air pressure ofapproximately 4 kg/cm², and conditions of the coating surface wereevaluated according to the following standards.

◯: an extent that scratches by impulse are slightly observed at aportion of a finishing coating layer.

Δ: an extent that scratches by impulse are observed, and peeling of thecoating layer reaches an under-coating layer.

x: an extent that damages by impulse are remarkable, and peeling area ofthe coating layer occupies not less than 10% of test area.

(9) Moisture resistance: Test piece was placed at an atmosphere of 50°C. and not less than 98% RH for 10 days, followed by conducting acrosshatched test.

Hereinafter, the graft copolymer of the No. VIII in the presentinvention and the coating composition containing thereof are morespecifically illustrated by Examples. Part is represented by part bymass.

Synthetic Examples VIII-1 and VIII-2 Synthesis of a Cellulose EsterDerivative

The cellulose ester derivatives obtained in the Synthetic Examples VII-1and VII-2 were employed.

Preparation of the Graft Copolymer (I)

Examples VIII-1

A reaction vessel equipped with an agitator, a thermometer, a condenser,and a dropping funnel was charged with 104 parts of butyl acetate and 10parts of the cellulose ester derivative obtained in the SyntheticExamples VII-1, followed by elevating temperature to 100° C. by heatingin a nitrogen stream. After confirmation of completely dissolving of thecellulose ester derivative, moisture in the cellulose ester derivativewas completely removed through a water separator by heating whilerefluxing.

Subsequently, at the same temperature, there were added dropwise over 3hours a mixed solution of polymerizable unsaturated monomers whichinclude 9 parts of styrene, 22.5 parts of methylmethacrylate, 9 parts of2-ethylhexyl acrylate, 13.5 parts of n-butylacrylate, 22.5 parts ofi-butylmethacrylate, and 13.5 parts of isocyanateethyl methacrylate, and3 parts of t-butylperoxy benzoate which is a polymerization initiator.Further, aging was continued at the same temperature for 2 hours toobtain a graft copolymer solution (I-1) having approximately 50% ofnonvolatile components. There are shown properties of the graftcopolymer solution obtained and the graft copolymer in Table VIII-1.

Examples VIII-2 to VIII-4 and Comparative Examples VIII-1 and VIII-2

The same procedures were followed as in the Examples VIII-1 except thatthe mixed solution composed of the cellulose ester derivatives obtainedin the Synthetic Examples VII-1 and VII-2, the polymerizable unsaturatedmonomers, and the polymerization initiator was changed to a mixedsolution shown in Table VII I-1 to obtain a graft copolymer solutions.(I-2) to (I-6). There are shown properties of the graft copolymersolution obtained and graft copolymer in Table VIII-1. TABLE VIII-1Comparative Feeding ratio and Physical properties of Graft ExampleExample copolymer (I) VIII-1 VIII-2 VIII-3 VIII-4 VIII-1 VIII-2 Solutionof Graft copolymer (I) I-1 I-2 I-3 I-4 I-5 I-6 Solvent, butyl acetate104 104 100 104 100 100 Derivative of a fatty Synthesis Example 10 30acid cellulose ester VIII-1 (a) Synthesis Example 10 10 20 VIII-2Polymerizable unsaturated monomer (b) Styrene Methyl methacrylate 9 9 98 10 2-ethylhexyl acrylate 22.5 27 19.8 7 20 25 n-butylacrylate 9 8Methylacrylate 13.5 9 13.5 7 25 i-butylmethacrylate 18 27 24n-butylmethacrylate 22.5 18 25 Isocyanateethyl methacrylate 20 13.5 272.7 58 15 Polymerization initiator t-butylperoxy benzoate 3 3 1.5 3 2.5Benzoil peroxide 2 Unvolatile components (%) 50 50 50 50 50 50 Viscosity(Gardner, 25° C.) ST V VX TU VW Q Mass average molecular weight 2500033000 53000 26000 30000 23000 Glass transition temperature (° C.) 36 5332 58 42 31 NCO group content (%) 3.7 7.3 0.7 15.2 — 4.1 (a)/(b) chain(mass ratio) 10/90 10/90 10/90 30/70 20/80 0/100Preparation of the Graft Copolymer (IV)

A reaction vessel equipped with an agitator, a thermometer, a condenser,and a dropping funnel was charged with 67 parts of xylene, followed byelevating temperature to 120° C. by heating while agitating, and therewere added dropwise over 3 hours a mixed solution of polymerizableunsaturated monomers which include 15 parts of “AA-6” (amethacryloyl-based macromonomer having methylmethacrylate as a segmentmanufactured by Toa Gosei Kagaku, Ltd.), 10 parts of styrene, 20 partsof methylmethacrylate, 30 parts of n-butylmethacrylate, and 15 parts ofisobutyl methacrylate, 10 parts of n-butylacrylate which are otherpolymerizable unsaturated monomers, and 3 parts oft-butylperoxy-2-ethylhexanoate which is a polymerization initiator.Further, aging was continued at the same temperature for 2 hours,followed by adding 15 parts of xylene to dilute and obtain a graftcopolymer (IV) solution having 55% of nonvolatile components.

Preparation of Non-Aqueous Dispersed Resin (V)

A reaction vessel equipped with an agitator, a thermometer, a condenser,and a dropping funnel was charged with 70 parts of xylene, followed byelevating temperature to 100° C. by heating while agitating, and therewere added dropwise over 3 hours a mixed solution of 10 parts ofstyrene, 25 parts of n-butylacrylate, 35 parts of isobutyl methacrylate,15 parts of t-butyl methacrylate, and 15 parts of2-ethylhexylmethacrylate, and 1.0 part of 2,2′-azobisisobutyronitrileand, aging was further continued at the same temperature for 2 hours,followed by adding 30 parts of xylene to dilute and obtain a polymersolution having 50% of nonvolatile components and viscosity of V whichis a stabilizer for dispersion.

Mass average molecular weight of the polymer was 45,000 and a glasstransition temperature was 45° C.

133 parts of the obtained polymer solution which is a stabilizer fordispersion and 85 parts of heptane were fed in a reaction vessel and refluxed while heating, and there were added dropwise over 3 hours a mixedsolution of 5 parts of styrene, 23 parts of methylmethacrylate, 6 partsof acrylonitrile, and 66 parts of methylacrylate, and 1.5 part of2,2′-azobisisobutyronitrile and, aging was further continued for 2 hoursto obtain a polymer emulsion having 52% of nonvolatile components andviscosity of EF which is a stabilizer for dispersion, and particlediameter of 0.3 μm in polymer particles, which is an opalescent andstable polymer dispersion.

Preparation of a Single-Liquid Type Clear Coating

Examples VIII-5 to VIII-14 and Comparative Examples VIII-3 to VIII-5

Single-liquid type clear coatings were prepared by mixing and agitatingthus-obtained graft copolymer solutions (I-1) to (I-6), thepolyisocyanate compounds, the cellulose ester derivatives, modifiedvinyl copolymers, the graft copolymer (IV), and the non-aqueousdispersed resin (V) according to formulation shown in Table VIII-3.

Subsequently, viscosity of the respective clear coatings was adjusted to13-14 seconds (Ford cup, #4/25° C.) by a thinner having the formulationratio of toluene/xylene/ethyl acetate/butyl acetate=50/20/10/20 by mass,followed by spray-coating onto a processed plate on which there arecoated in order a commercially-supplied lacquer primer, a lacquer primersurfacer, and a metallic base coating at room temperature (20° C.), sothat a coating layer having the thickness of 40 μm is formed afterdried. Table VIII-2 collectively shows results of performance tests bythe coatings. TABLE VIII-2 Composition of a clear coating and ExampleComparative Example performance test VIII-5 VIII-6 VIII-7 VIII-8 VIII-9VIII-10 VIII-11 VIII-12 VIII-13 VIII-14 VIII-3 VIII-4 VIII-5 Solution ofa graft copolymer (I) I-1 100 90 90 90 I-2 100 I-3 100 90 90 100 I-4 100I-5 10 100 I-6 10 100 10 Solution of a graft 10 90 copolymer (IV)Nonaqueous resin 10 dispersion (V) Polyisocyanate 5 compound (note 1)Oxazoline compound 0.75 (note 2) Catalyst A for 0.015 0.015 0.015 0.0150.015 0.015 0.015 0.015 0.015 0.015 0.015 curing (note 3) Catalyst B for0.008 curing (note 4) Thinner 11 11 11 11 11 11 12 11 16 12 11 11 11Nonvolatile 45 45 45 45 45 45 45 45 45 45 45 45 45 components in acoating (% by mass) Dryability (sec) 90 60 90 30 60 90 60 60 60 60 120270 180 Hardness 1 day 4.2 6.6 3.9 7.0 4.5 3.9 4.5 4.5 3.8 3.9 2.0 3.13.0 of a 7 days 9.2 10.7 8.8 11.0 9.2 9.0 9.2 9.4 9.1 9.1 3.3 3.5 8.0coating layer Outer appearance ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Δ Δ X after finishingAccelerated ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ X ◯ X weatherability Storage stability ◯◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

It is to be noted that (note 1)-(note 2) and experimental methods in theTable VIII-2 are as follows.

(note 1) Polyisocyanate compound: “N-3500” which is an isocyanurate typeone of hexamethylene diisocyanate manufactured by Sumitomo BayerUrethane, Ltd., and which has nonvolatile components of 100%, NCO groupcontent of 21.6%.

(note 2) Oxazolidine compound: “Incozol LV” manufactured by IndustrialCopolymer, Ltd., and which has a purity of 99%.

(note 3) Catalyst A for curing: dibutyltin dilaurate

(note 4) Catalyst B for curing: diisopropyl phosphate

Experimental Methods

Dryability: After coated at 20° C. and a coated plate was horizontallymaintained for 20 minutes, it was placed at the temperature of 20° C.and humidity of 75% RH in an air-conditioned room, and 8 pieces of gauzewere put one upon another on surface of coating layer, and the weight of200 g having contact area of 12.56 cm² was put on the gauze. There wasmeasured a placing time of period (second) during which the gauze doesnot completely leave marks.

Hardness of coating layer: After coated at 20° C. and a coated plate washorizontally maintained for 20 minutes, it was placed at the temperatureof 20° C. and humidity of 75% RH in an air-conditioned room for 1 day or7 days, and Toucon hardness of the coating layer was measured under acondition of 20° C. using a Toucon hardness meter manufactured byAmerican Chain & Cable Company. A larger value is harder.

Finishing state: After coated at 20° C. and a coated plate washorizontally maintained for 20 minutes, it was placed at the temperatureof 20° C. and humidity of 75% RH in an air-conditioned room for 1 day,and smoothness, a build-feeling, and transparency in the coating layeron the plate were visually judged.

-   -   ◯: excellent    -   Δ: slightly worse    -   x: worse

Accelerated weatherability: After coated at 20° C. and a coated platewas horizontally maintained for 20 minutes, it was placed at thetemperature of 20° C. and humidity of 75% RH in an air-conditioned roomfor 7 days, and there was observed the presence or the absence of achange in the coating layer after placing the coated plate for 1000hours in a sunshine weather-o-meter.

-   -   ◯: Surface of the coating layer is not almost changed.    -   x: Water marks are observed on the surface of the coating layer.

Storage stability: A coating having nonvolatile components of 45% wassealed up and stored at 40° C. for 6 months and, subsequently, aviscosity change was measured.

-   -   ◯: Viscosity change was not almost observed.    -   Δ: Viscosity was slightly changed.    -   x: Viscosity remarkably increased, or gelation was caused.

Hereinafter, the lactide/lactone copolymer of the No. IX in the presentinvention and the method for the preparation thereof is morespecifically illustrated by Examples.

Molecular weight represents a value based on a Polystyrene measured byGPC. An average continuous chain length in respective units wascalculated by integrated values of carbonyl carbon in ¹³C-NMR accordingto a report [Makromol. Chem. 194, 913-925 (1993)] by Kasperczyk, et al.For references, FIG. 8 shows a ¹³C-NMR chart after a termination of astep 1 in Example IX-3, and FIG. 9 shows a ¹³C-NMR chart after atermination of a step 2 in Example VIII-3.Average continuous chain length in lactide unit(1LL)=½*[LLL+LLC+CLL+CLC]/[CLC+½*(LLC+CLL)]

-   -   Wherein, LLL, LLC, CLL, and CLC are as follows.    -   LLL=½*[CapLLLL]+½*[LLLLCap]+⅓*[CapLLLCap]+[LLLLLL]    -   LLC=½*[CapLLCap]+½*[LLLLCap]+⅓*[CapLLLCap]    -   CLL=½*[CapLLCap]+½*[CapLLLL]+⅓*[CapLLLCap]    -   CLC=[CapLCap]        Average continuous chain length in lactone unit (1        Cap)=[LCL+CCL+LCC+CCC]/[LCL+½*(CCL+LCC)]    -   Wherein, LCL, CCL, LCC, and CCC are as follows.    -   LCL=[LLCapLL]+[LLCapLCap]+[CapLCapLL]+[CapLCapLCap]    -   CCL=[CapCapLCap]+[CapCapLL]    -   LCC=[CapLCapCap]+[LLCapCap]    -   CCC=[CapCapCap]

Carbonyl carbons of the respective units in ¹³C-NMR spectrum areassigned as follows.

-   -   CapLLLL, LLLLLL: 169.6 ppm; (CapLLLCap: 169.65 ppm); LLLLCap:        169.7 ppm    -   CapLLLL: 170.1 ppm; (CapLLLCap: 170.15 ppm); CapLLCap: 170.2 ppm    -   (CapLLLCap,): LLLLCap: 170.3 ppm; CapLCap: 170.8 ppm    -   (CapLCapLCap, LLCapLCap: 172.7 ppm); LLCapLL: 172.75 ppm    -   CapCapLL: 172.8 ppm; LLCapCap: 173.4 ppm    -   (CapLCapCap: 173.45 ppm); CapCapCap: 173.5 ppm

In the above descriptions, Cap represents caproyl unit, even-numberedpieces of LL represent lactydyl unit, odd-numbered pieces of Lrepresents one piece of lactyl unit and lactydyl unit. Values in ( ) arevalues for reference.

After measuring the average continuous chain length at a period oftermination of respective steps, an average continuous chain length in arandom or block portion was decided. According to the method for thepreparation of the present invention, since there is not a restructuringof units constructed at a prior step by transesterification reaction,the average continuous chain length in a block portion is decided by acalculation as shown below.1LL(B)=[1LL(2)−F ₁1LL(1)]/F ₂[wherein, 1LL(B) represents the average continuous chain length oflactide units in a block portion, 1LL(1) represents the averagecontinuous chain length of lactide units at termination of the step 1,1LL(2) represents the average continuous chain length of lactide unitsat termination of the step 2, F₁ represents a lactide amount fed in thestep 1, and F₂ represents a lactide amount fed in the step 2]

Tensile test was according to JIS K7113.

DCS measurement was conducted at a temperature elevation speed of 10°C./min.

Comparative Example IX-A

A lactide/caprolactone (=60/40) copolymer was synthesized at 180° C. byadding 138.4 g (960.2 mmol) of a lactide monomer (water content of 70ppm, an acid value of 0.12 mgKOH/g), 70.9 ml (639.8 mmol) of acaprolactone monomer (water content of 70 ppm, an acid value of 0.10mgKOH/g), 89.0 ml (1.6 mmol) of ethylene glycol which is an initiator,and 0.26 ml (0.8 mmol) of tin octylate which is a catalyst.

A molecular weight of the copolymer obtained was 97,300, the averagecontinuous chain length of lactide units was 3.3, the average continuouschain length of lactone units is 1.8, and Tg was 13.2° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 4 kgf/cm², tensile strength was notless than 12 kgf/cm², and elongation at rupture was not less than1,700%.

Further, in a polymer sampled on the way of a reaction, total conversionwas 56.5%, conversion of lactide was 98.5%, 1LL was 85.7, and 1cap was1.9. From the results, it is understood that a transesterificationreaction is caused on the way of the reaction in the copolymer obtainedby the synthesis method and, structures as shown in the presentinvention are contained only in a low content. Low elasticity shows afact.

Comparative Example IX-B

A lactide/caprolactone (=60/40) copolymer was synthesized at 150° C. byadding 138.4 g (960.2 mmol) of a lactide monomer (water content of 70ppm, an acid value of 0.12 mgKOH/g), 70.9 ml (639.8 mmol) of acaprolactone monomer (water content of 70 ppm, an acid value of 0.10mgKOH/g), 89.0 ml (1.6 mmol) of ethylene glycol which is an initiator,and 0.26 ml (0.8 mmol) of tin octylate which is a catalyst.

A molecular weight of the copolymer obtained was 97,900, the averagecontinuous chain length of lactide units was 3.9, the average continuouschain length of lactone units is 2.0, and Tg was 4.3° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 7 kgf/cm², tensile strength was notless than 20 kgf/cm², and elongation at rupture was not less than2,050%.

Further, in a polymer sampled on the way of a reaction, total conversionwas 59.2%, conversion of lactide was 98.5%, 1LL was 6.9, and 1cap was2.2. From the results, it is understood that a transesterificationreaction is caused on the way of the reaction in the copolymer obtainedby the synthesis method and, structures as shown in the presentinvention are contained only in a low content. Low elasticity shows afact.

Comparative Example IX-C

A lactide/caprolactone (=60/40) copolymer was synthesized at 180° C. byadding 70.9 ml (639.8 mmol) of a caprolactone monomer (water content of70 ppm, an acid value of 0.10 mgKOH/g) and 0.25 ml (1.6 mmol) of octanolwhich is an initiator, and 0.26 ml (0.8 mmol) of tin octylate which is acatalyst, followed by adding 138.4 g (960.2 mmol) of a lactide monomer(water content of 70 ppm, an acid value of 0.12 mgKOH/g) while furtheragitating at 180° C.

A molecular weight of the copolymer was 60,000, the average continuouschain length of lactide units was 153.6, the average continuous chainlength of lactone units is 31.4, Tg was −68.2° C., and Tm was 55.9° C.and 164.8° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 2844 kgf/cm², tensile strength was56 kgf/cm², and elongation at rupture was not less than 2.4%.

Comparative Example IX-D

A lactide/caprolactone (=60/40) copolymer was synthesized at 180° C. byadding 70.9 ml (639.8 mmol) of a caprolactone monomer (water content of70 ppm, an acid value of 0.10 mgKOH/g) and 89.0 ml (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst, followed by adding 138.4 g (960.2 mmol) ofa lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g) while further agitating at 180° C.

A molecular weight of the copolymer was 30,000, the average continuouschain length of lactide units was 40.4, the average continuous chainlength of lactone units is 39.3, Tg was −68.5° C., and Tm was 56.5° C.and 162.0° C.

A sheet having thickness of 2 mm molded from the copolymer by acompression molding is very brittle, and tensile strength wasimpossible.

Comparative Example IX-E

A polymerization was conducted by adding 138.4 g (960.2 mmol) of alactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 106.4 ml (960.2 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 0.368 ml (2.4 mmol) ofdiethylaluminum ethoxide which is an initiator at 75° C. inchlorobenzene for 280 hours. A copolymer was precipitated by hexane froma solution obtained, and dried at 50° C. in vacuo.

Yield of the copolymer obtained was 74.0%, and a molecular weight was97,500. The average continuous chain length of lactide units was 6.7,and the average continuous chain length of lactone units was 3.2.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 18 kgf/cm², tensile strength was 28kgf/cm², and elongation at rupture was not less than 920%.

Further, in a copolymer sampled on the way of a reaction, totalconversion was 53.3%, conversion of lactide was 90.7%, 1LL was 15.3which is the average continuous chain length of lactide units, and 1capwas 2.5 which is the average continuous chain length of lactone units.From the results, it is understood that a transesterification reactionis caused on the way of the reaction in the copolymer obtained by thesynthesis method and, structures as shown in the present invention arecontained only in a low content. Low elasticity shows a fact.

Example IX-1

Polymerization was conducted at 180° C. by adding 13.84 g (96.02 mmol)of a lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 70.9 ml (639.8 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 89.0 ml (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst, followed by adding 124.6 g (864.2 mmol) ofa lactide monomer so that total molar ratio of lactide/caprolactone isadjusted to 60/40 while further agitating at 180° C. to synthesize alactide/caprolactone (=60/40) copolymer.

Molecular weight of the copolymer obtained was 84,300, the averagecontinuous chain length of lactide units was 12.5, the averagecontinuous chain length of lactone units is 5.9, Tg was −47.5° C., andTm was 42.1° C. and 164.0° C. Further, at a period of termination of thestep 1, 1LL(1) was 1.3 which is the average continuous chain length oflactide units, and 1Cap (1) was 5.9 which is the average continuouschain length of lactone units. From the results, it was confirmed that1LL(R) is 1.3 which is the average continuous chain length of lactideunits of a random portion, and 1LL(B) is 13.7 which is the averagecontinuous chain length of lactide units of a block portion.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 920 kgf/cm², tensile strength was 41kgf/cm², and elongation at rupture was 8.9%.

Example IX-2

Polymerization was conducted at 180° C. by adding 41.52 g (288.06 mmol)of a lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 70.9 ml (639.8 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 89.0 ml (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst, followed by adding 96.9 g (672.1 mmol) ofa lactide monomer so that total molar ratio of lactide/caprolactone isadjusted to 60/40 while agitating at 180° C. to synthesize alactide/caprolactone (=60/40) copolymer.

Molecular weight of the copolymer obtained was 83,900, the averagecontinuous chain length of lactide units was 5.5, the average continuouschain length of lactone units is 3.0, Tg was −29.1° C., and Tm was152.0° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 239 kgf/cm², tensile strength was 26kgf/cm², and elongation at rupture was 870%.

Example IX-3

Polymerization was conducted at 180° C. by adding 69.2 g (480.1 mmol) ofa lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 70.9 ml (639.8 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 89.0 ml (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst, followed by adding 69.2 g (480.1 mmol) ofa lactide monomer so that total molar ratio of lactide/caprolactone isadjusted to 60/40 while further agitating at 180° C. to synthesize alactide/caprolactone (=60/40) copolymer.

Molecular weight of the copolymer obtained was 86,000, the averagecontinuous chain length of lactide units was 4.7, the average continuouschain length of lactone units is 2.3, Tg was −14.0° C., and Tm was138.0° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 70 kgf/cm², tensile strength was notless than 63 kgf/cm², and elongation at rupture was not less than 1220%.

Example IX-4

A polymerization was continuously conducted at 180° C. by adding 692 g/h(4.8 mol/h) of a lactide monomer (water content of 70 ppm, an acid valueof 0.12 mgKOH/g), 709 ml/h (6.4 mol/h) of a caprolactone monomer (watercontent of 70 ppm, an acid value of 0.10 mgKOH/g), and 1.1 g/h (5.3mmol/h) of aluminum isopropoxide which is an initiator through anextruder type reactor, followed by adding 692 g/h (4.8 mol/h) of alactide monomer so that total molar ratio of lactide/caprolactone isadjusted to 60/40 at 180° C. to further polymerize alactide/caprolactone (=60/40) copolymer.

Molecular weight of the copolymer obtained was 86,000, the averagecontinuous chain length of lactide units was 4.6, the average continuouschain length of lactone units is 2.3, Tg was −13.8° C., and Tm was135.7° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 71 kgf/cm², tensile strength was notless than 68 kgf/cm², and elongation at rupture was not less than 1320%.

Example IX-5

Polymerization was conducted at 180° C. by adding 41.52 g (288.06 mmol)of a lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 49.6 ml (447.9 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 89.0 μl (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst, followed by adding 96.9 g (672.1 mmol) ofa lactide monomer and 21.3 ml (191.9 mmol) of a caprolactone monomer sothat total molar ratio of lactide/caprolactone is adjusted to 60/40while further agitating at 180° C. to synthesize a lactide/caprolactone(=60/40) copolymer.

Molecular weight of the copolymer obtained was 85,100, the averagecontinuous chain length of lactide units was 5.1, the average continuouschain length of lactone units is 3.4, Tg was −33.8° C., and Tm was158.1° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 22 kgf/cm², tensile strength was notless than 35 kgf/cm², and elongation at rupture was not less than 1200%.

Example IX-6

Polymerization was conducted at 180° C. by adding 41.52 g (288.06 mmol)of a lactide monomer (water content of 70 ppm, an acid value of 0.12mgKOH/g), 49.6 ml (447.9 mmol) of a caprolactone monomer (water contentof 70 ppm, an acid value of 0.10 mgKOH/g), and 89.0 μl (1.6 mmol) ofethylene glycol which is an initiator, and 0.26 ml (0.8 mmol) of tinoctylate which is a catalyst.

Subsequently, 21.3 ml (191.9 mmol) of a caprolactone monomer was added,and 96.9 g (672.1 mmol) of a lactide monomer was added so that molarratio of lactide/caprolactone is adjusted to 60/40 while agitating at180° C. to synthesize a lactide/caprolactone (=60/40) copolymer havingtotal molar ratio of lactide/caprolactone 60/40 at a termination periodof polymerization.

Molecular weight of the copolymer obtained was 82,000, the averagecontinuous chain length of lactide units was 5.7, the average continuouschain length of lactone units is 3.7, Tg was −13.3° C., and Tm was 56.8°C. and 152.1° C.

In a sheet having thickness of 2 mm molded from the copolymer by acompression molding, elasticity was 305 kgf/cm², tensile strength was 37kgf/cm², and elongation at rupture was not less than 380%.

The above results are shown in Table IX-1. TABLE IX-1 1 LL 1 CapExtention (1) (1) Molecular Tensile at 1 LL 1 LL weight 1 LL 1 CapEleasticity Strength fracture Tg (B) (R) Comparative 97,300 3.3 1.84 >11 >1700 13.2 Example IX-A Comparative 97,900 3.9 2.0 7 >20 >2050 4.3Example IX-B Comparative 60,000 153.6 31.4 2844 56 2.4 −68.2 ExampleIX-C Comparative 30,000 40.4 39.3 — — — −68.5 Example IX-D Example IX-184,300 12.5 5.9 920 41 8.9 −47.5 1.3 5.9 13.7 1.3 Example IX-2 83,9005.5 3.0 239 26 870 −29.1 1.8 3.1 7.1 1.8 Example IX-3 86,000 4.7 2.370 >68 >1220 −14.0 2.4 2.5 7.0 2.4 Example IX-4 80,900 4.6 2.371 >68 >1320 −19.8 3.6 2.5 6.9 3.6 Example IX-5 85,100 5.1 3.422 >35 >1200 13.8 3.1 3.7 6.0 8.1 Example IX-6 82,000 5.7 3.7 305 37 380−13.3 1.9 2.1 7.3 1.9

Unit: In the elasticity and tensile strength, it is kgf/cm², in theelongation at rupture, it is %, and, in the glass transition temperatureTg, it is ° C.

A number average continuous chain length: 1LL(1) is the length of thelactide unit at a termination period of the step 1, 1Cap(1) is thelength of the lactone unit at a termination period of the step 1, 1LL isthe length of the lactide unit at a termination period of the step 2,1Cap is the length of the lactone unit at a termination period of thestep 2, 1LL(B) is the length of the lactide unit in a block portion, and1LL(R) is the length of the lactide unit in a random portion.

Possibility of Utilization in Industry

According to the No. I in the present invention, there can becomereadily designed aliphatic polyesters having a controlled thermaldecomposition property, hydrolizability, and biodegradability withoutaffecting to other physical properties, and there is provided a methodfor the preparation of such the aliphatic polyesters.

In the particle-state composition for agriculture and gardening of theNo. II in the present invention, biodegradability in a coating thinlayer can become appropriately and selectively lowered, a durationperiod of time a fertilizing effect can be controlled, and the coatingthin layer is disintegrated and decomposed by microorganisms in soilafter elution of a fertilizer, whereby, it is not remained in soil.Further, it has an effect that residual components disappear after acultivation period of farm products by disintegration and decompositionof the coating thin layer, and it becomes easy to control a supply ofthe fertilizer.

In the particle-state composition for agriculture and gardening of theNo. III in the present invention, operability of solvent is excellent ina period of formation of a coating thin layer, and a duration period oftime of a fertilizing effect can be controlled in the particle-statecomposition for agriculture and gardening obtained, and the coating thinlayer is disintegrated and decomposed by microorganisms in soil afterelution of a fertilizer, whereby, it is not remained in soil. Further,it has an effect that residual components disappear after a cultivationperiod of field products by disintegration and decomposition of thecoating thin layer, and it becomes easy to control a supply of thefertilizer.

In the base film for a marking film of the No. IV in the presentinvention, there is employed an aliphatic cellulose ester derivativeobtained by a ring-opening graft polymerization of a cyclic ester with afatty acid cellulose ester having hydroxyl groups. And, it does notcontain additives having a migrating property compared to conventionalpublicly-known mixed-type plasticizers having a low or high molecularweight, it is most appropriate as utilization for the derivative.

By the use of the heat-sensitive transfer picture image recordingmaterial formed by the cyclic ester-modified cellulose ester derivativeof the No. V in the present invention, there can be obtained a printedpicture image having a high coloring concentration while maintaining astrippability.

By setting up the heat-resistible protecting layer composed of thecyclic ester-modified cellulose ester derivative of the No. VI in thepresent invention onto an opposite surface to surface having aheat-transfer ink layer in a substrate, the following excellent effectscan be obtained, and an excellent printing quality can be obtained. (i)Occurrence of a sticking phenomenon can be sufficiently prevented. (ii)There can be suppressed occurrence of a migrating phenomenon ofconstructing components in the heat-resistible protecting layer toward asurface of an ink layer and a blocking phenomenon even in the case ofstoring a heat-sensitive transfer picture image recording medium for along period of time or under a high temperature in a roll state. (iii)Staining of a thermal head is suppressed which is caused by theheat-resistible protecting layer shaved by an abrasion force with thethermal head.

In the conductive coating composition of the No. VII in the presentinvention in which there are mixed a conductive carbon black and a scalygraphite in a specified proportion, since the scaly graphite is not aptto be separated from resin components and to precipitate, there is shownan effect that it is excellent in storage stability for a long time ofperiod and, since those connect each other, there can be repeatedly andefficiently obtained an effect that it elevates conductivity in acoating layer.

By the use of a cellulose ester derivative obtained by a ring-openinggraft polymerization of a cyclic ester with a cellulose ester havinghydroxyl groups, since there is shown an effect that contact of thescaly graphite itself is often caused and conductivity in a coatinglayer is elevated by connection of the scaly graphite with the scalygraphite, there can be formed a coating layer which is excellent inadhesion to an article to be coated and a finishing coating, and whichis excellent in conductivity.

According to the No. VIII in the present invention, there can beobtained a moisture-curable type graft copolymer which is useful for asingle-liquid type coating and a sealing agent, and a coatingcomposition containing the copolymer, in which there is not a problemsuch as a toxicity and an irritative property, and which is excellent indryability and does not deteriorate physical properties in a coatinglayer.

According to the No. IX in the present invention, there can be obtaineda lactide/lactone copolymer which is excellent in a heat resistance andan impact resistance, and there can be stably obtained the copolymer ina low cost.

1-31. (canceled)
 32. A heat-transfer recording medium which comprisessetting up a heat-transfer ink layer on the surface of a supportingmaterial, and setting up a heat-resistible protecting layer on the othersurface of the substrate, and in which the heat-resistible protectinglayer is composed of a cyclic ester-modified cellulose derivativeobtained by a ring-opening graft-polymerization of a cyclic ester to acellulose derivative having hydroxyl groups.
 33. A heat-transferrecording medium claimed in claim 32, wherein the cellulose derivativehaving hydroxyl groups is a cellulose acetate.
 34. A heat-transferrecording medium claimed in claim 32, wherein the cyclic ester isε-caprolactone. 35-55. (canceled)